Jouhaux was born to a family with radical traditions. At 16, he entered a match factory where he joined a trade union movement. His career as a trade union member advanced quickly as he demonstrated organisational skills, strong personality and oratory talents. In 1909, he became Secretary General of the General Confederation of Labour (CGT).

Before the Second World War, he organised a number of mass protests. Under his leadership, CGT developed a peace programme pleading to limit arms, introduce international arbitration, respect nationality and end secret treaties. In 1916, Jouhaux presented a report that laid the foundation for the establishment of the International Labour Organisation; in 1919, he was elected as one of the worker representatives of the ILO in Geneva.

He was member of the French delegation to the League of Nations (1925–1928) and the United Nations (1946–1951) where he advocated for the recognition of the right to association. In 1949, he became President of the European Movement, and in 1947 – the Chair of C.G.T.-Force Ouvriere, supporting the establishment of the United States of Europe and the association of workers from all over the world.