Mr. Puig grew up atop the company’s offices and factory, in a six-story building in the Eixample district where a noisy dumbwaiter carried packages to the street and large tanks of alcohol sat in the basement. After visiting the vats in his youth, going downstairs with his father to learn the science behind perfume, he earned a chemical engineering degree and began working full time for the family business.

Decades later, he admitted that he never had a good nose for fragrances. Instead he possessed a talent for cutting deals that transformed Puig, the company that bears his family’s name, into a fashion and fragrance powerhouse. Jetting around the world with a suitcase filled with soaps and perfumes, he negotiated licensing arrangements and acquisitions with top designers such as Paco Rabanne and Carolina Herrera.

Mr. Puig, who was only 29 when he took the reins of Puig in 1957, led the company with help from his three brothers until retiring as chief executive more than four decades later. He was 93 when he died April 13 at a hospital in Barcelona, according to company spokeswoman Emmanuelle Durand, who did not give a precise cause.

By the time Mr. Puig stepped down as CEO in 1998, Puig was one of the few family-run businesses remaining in the luxury-goods industry, which is dominated by corporate conglomerates such as LVMH. “Our competitors just five years ago were family companies and had the names of their founders on the door, but walls disappear, markets evolve,” he said in a farewell speech. “Only 15 percent of companies survive the transition from the second to the third generation.”

It remained a point of pride for Mr. Puig that his business weathered that changeover and continued to thrive. The company is run by his son Marc and has grown to include brands such as Isdin, Charlotte Tilbury, Jean Paul Gaultier, Penhaligon’s, Dries Van Noten, Uriage, Apivita, L’Artisan Parfumeur and — through a licensing agreement — Christian Louboutin. In 2019, it reported sales of 2 billion euros, or about $2.4 billion.

While Mr. Puig’s older brother, Antonio, focused on creative and design issues, Mr. Puig spearheaded the company’s expansion abroad, opening a U.S. subsidiary in the 1960s to bring Puig’s fragrances and soaps to department stores including Saks Fifth Avenue, Marshall Field and Neiman Marcus. He also began negotiating with Rabanne after deciding that the company “needed a French product coming from Paris” to break into the American market, as he later told Women’s Wear Daily.

The designer was by then known as the enfant terrible of French fashion; he had created a futuristic collection titled “Twelve Unwearable Dresses,” and when he met with Mariano and Antonio Puig in his office for the first time, he offered them a seat on stools made from bicycle saddles. “They seemed very modern to me. They wanted a name that was ‘virgin’ in the field of perfumery,” Rabanne later told Eugenia de la Torriente, author of the 2014 corporate history “Puig: 100 Years of a Family Business.”

Their collaboration got off to a difficult start. Shortly after signing a contract with Rabanne in May 1968, Mr. Puig and his brother went looking for Champagne to celebrate. Walking through Paris, they found themselves in the middle of violent student protests, with cars burning and barricades in the streets. Trying to capture the spirit of the times, Rabanne suggested a fragrance that smelled like metal and a bottle shaped like a screw.

Those ideas evolved into Calandre, a hit perfume with a floral scent and a distinctive, square-cornered bottle — inspired by the U.N. tower in Manhattan — that Rabanne sketched on a paper tablecloth over dinner with Mr. Puig. “It was a great success in this period. We didn’t have the money to buy competitive companies, but we felt ourselves able to create something,” Mr. Puig told Women’s Wear Daily in 2014. “We defined ourselves as being brand-builders.”

Mr. Puig acquired Rabanne’s fashion and accessories lines in 1987. Around that same time, he signed an agreement to produce perfumes by Herrera, a Venezuelan designer who had risen to prominence in New York. She later told the website Business of Fashion that she backed out of another licensing deal after meeting Mr. Puig at a party at her home, inspired partly by his company’s approach to business.

“Family businesses give me confidence,” she said. “It’s very steady — how it should be.”

The second of four sons, Mariano Puig Planas was born in Barcelona on Dec. 8, 1927. His father, Antonio, founded Puig in 1914. During the Spanish Civil War, Mr. Puig left town with his siblings and mother, a homemaker, taking refuge at a tuberculosis sanitarium founded by his aunt. The family company was collectivized during the war, with the elder Puig staying on as a worker, according to the 2014 corporate history.

As a young man, Mr. Puig was a champion water skier; he later served as president of the Spanish Waterskiing Federation and helped organize the 1971 World Championships in Banyoles, Spain. He went to Geneva at age 18 to learn from the perfume company Givaudan, graduated from the Chemical Institute of Sarrià and took on growing management duties at Puig beginning in the 1950s.

His father, who died in 1979, insisted that Mr. Puig and his brothers work together while running the business. “We have never made an important decision without dialogue, by telephone, during weekends, or in a more formal fashion,” Mr. Puig later said. “We have not always been in agreement, but we have always come to an agreement.”

Mr. Puig graduated in 1964 from the IESE Business School, part of the University of Navarra. He later recalled that his decision to expand Puig was driven partly by his collaboration with Max Factor Jr., whom he met in the early 1970s after traveling to Los Angeles with his wife, María Guasch. Together they persuaded the American cosmetics executive to let Puig distribute Max Factor products in Spain.

“That is how I learned what it means to be a multinational company, and I learned manufacturing and marketing techniques that were very useful to us,” he said. “Spain was small and closed, and that made me think about what we wanted to do and be.”

Survivors include his wife, whom he married in 1954; five children, Marc, Marian, Ana, Ton and Daniel; and nine grandchildren.

In his last years as CEO, Mr. Puig acquired Herrera’s fashion business and bought the Paris fashion and fragrance house Nina Ricci. He served as chairman of Puig’s holding company until 2003 and was president of the Puig Foundation until 2014. He was also a founding member and former president of the Family Business Institute in Spain.

Mr. Puig generally shunned the spotlight, giving few interviews but appearing at perfume conferences, where he was sometimes asked about the industry’s future. He was typically optimistic — he had seen his father lead Puig through the Spanish Civil War, World War II and the difficult period that followed, when Spain was isolated from the international economy under Franco’s regime. It was difficult to sell anything in those years, but the business had survived.

“In times of crisis,” he once said at a conference panel in Paris, “you may not buy an apartment or a new car, but you always have enough to buy perfume — or let’s hope so.”