Born in London to Irish parents, Edward left school when his father died to take care of himself and his mother. He showed promise as a painter and illustrator from an early age and he began his career as a sketch artist for The Smart Set magazine.
Lady Duff-Gordon, the British couturier and owner of Maison Lucile spotted his talents in 1910 and she employed him as a sketcher in her London salon. Because of his talent and ability, he found himself rising quickly to the role of assistant designer at the house's Paris premises in 1911 at the age of 20. He also worked in her salons in New York and Chicago.
At the start of the First World War, Molyneux joined the Duke of Wellington Regiment. He achieved some fame in his military career, later receiving the British Military Cross, and was subsequently always referred to as Captain Molyneux. His wounds from the war eventually lead to the loss of vision in his left eye. Molyneux returned to work for Maison Lucille after the war, but in 1919 opened his own fashion house on the Rue Royale in Paris, which was an almost immediate success.
Molyneux expanded his business first to Monte Carlo and Cannes and later to London by 1933. His clientele at the Grosvenor Street salon included actresses as well as members of the British Royal family. One of his most famous designs was the wedding dress of Princess Marina, Duchess of Kent. Examples of Molyneux designs can now be found in the collections of the Victorian and Albert Museum in London, the Boston Museum of Fine Arts, and the Costume Institute of the Metropolitan Museum of Art in New York.
With partner Elsa Maxwell, Molyneux opened in 1921 a Paris nightclub, Les Acacias; the partners later opened another club, Le Jardin de ma soeur. In 1923 Molyneux married Muriel Dunsmuir, daughter of the Lieutenant Governor of British Columbia; the marriage lasted one year.
Molyneux was in France until just prior to the fall of Paris, when he left for England from Bordeaux, via a coal barge. The Paris salon was kept open during the occupation and Molyneux returned to it as soon as possible after the war. However, he soon retired on the advice of his doctors, fearing the loss of his remaining eyesight.
Molyneux made a brief comeback in 1964 but after a few seasons he retired again and gave the responsibility for the biannual collections to John Tullis, a cousin who had worked in the Paris salon before the war.
Molyneux was an avid collector of art, first acquiring eighteenth century French paintings and later the Impressionists. His collection, featured in a 1952 exhibition held in New York and Washington, was purchased in 1955 by Ailsa Mellon Bruce [1901-1969], whose collection was left to the National Gallery of Art at her death.Molyneux also painted throughout his life. Exhibitions of his paintings were held at the Galerie Weill in Paris in the early 1950’s and at the Hammer Galleries in New York in the late sixties where ‘Carnations in Vase’ was purchased by the Duke and Duchess of Windsor, and Greta Garbo ‘Roses in Glass’. Molyneux was a chevalier of the Legion of Honor.Keeping up with the radical new sensibilities influencing the worlds of art, culture and ideology at the time, Molyneux developed a refined, modern style, dispensing with superfluous flourishes in favour of striking simplicity. One of the most highly-regarded designers of his day, his work influenced the likes of Christian Dior and Pierre Balmain. He soon became a high society favourite, dressing European royals like Princess Marina of Greece and Denmark (who became the Duchess of Kent), as well as silver screen stars including Greta Garbo, Marlene Dietrich and Vivien Leigh. Moving in such circles meant Molyneux had a coterie of glamorous friends, including the playwright Noël Coward, as well as the similarly literary Mitford sisters. After his retirement from the fashion industry, Molyneux divided his time between homes in Jamaica, New York and the French Riviera. He died in Monte Carlo in March of 1974 and is buried in the French town of Biot, where he had a home, leaving a memorable imprint on the fashion and art landscapes behind him.