Jouhaux's father worked in a match factory in Aubervilliers. His secondary schooling ended when his father's earnings were stopped by a strike. He gained employment at the factory at age sixteen and immediately became an important part of the union. In 1900, he joined a strike against the use of the white phosphorous that had sent his father blind, and was dismissed, and worked at a succession of jobs until union influence saw him reinstated.
In 1906, he was elected by the local union as a representative to the Confédération générale du travail, where his abilities saw him quickly rise through the ranks of organized labour. By 1909 he became interim treasurer, and shortly afterwards became secretary-general of the organization, which he held until 1947.
In the years before First World War, Jouuhaux organised several mass protests, and the organization he led protested against the war. However, once the war started, Jouhaux supported his country and believed that a Germany victory would led to the destruction of democracy in Europe. During World War II he was arrested and imprisoned by Nazi Germany.
His goals as a trade unionist were the familiar ones of the early labour movement - the eight hour day, the right to union representation and collective bargaining, and paid holidays. The 1936 Matignon Agreement, to which he was a signatory, awarded many of these rights to French workers.
In an international context, his work was instrumental in the setting up of the International Labor Organization (ILO), and was elected to high positions in international trade union bodies, including the International Federation of Trade Unions and its postwar kin the World Federation of Trade Unions until that body split.