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Edward Molyneux changed the course of his life by debuting his design house in 1919 after perfecting his skills at the Lucile house of fashion. His quick success led him to open several satellite boutiques in France. In 1925, he expanded his operations into Monte Carlo, and in 1932, into London. His opulent, long line women's evening wear designs adorned many celebrities of the day, including Vivien Leigh, Greta Garbo, Margaret Leighton, and Gertrude Lawrence. He also outfitted numerous members of British High Society and European royalty. His contemporaries, Pierre Balmain and Christian Dior, were fans of his work. Molyneux served as an infantry captain for the British Forces during World War II. He retired from his eponymous design house in 1950, leaving designer Jacques Griffe as the head of operations. In 1964, he came out of retirement, founding the ready-to-wear Studio Molyneux. After receiving numerous mixed reviews, he closed the studio in 1974.

In 1925, Molyneux debuted his first women's fragrance, Le Numero Cinq. According to rumors of the day, he and Coco Chanel simultaneously released 'Number Five' fragrances to see which designer's scent would ultimately experience the most success. While no one has ever been able to confirm the myth, Molyneux did indeed rename his fragrance La Parfum Connu. As of 2014, Molyneux's fragrance line is operated by Perfume Berdoues, who offers 14 women's and men's fragrances under the designer's label.

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