He studied medicine in Rouen and Paris, where he learned clinical education at several hospitals. He developed an interest in neurology, and his first important scientific work involved lesions of the plexus brachialis. He earned his medical doctorate at Paris in 1898.
He later became chef de clinique for nervous disease, and in 1910 acquired his agrégation. After the end of World War I, he worked at Charité Hospital in Paris, followed by a professorship of neurology at the Salpêtrière (1923).
Guillain was a prolific writer, in 1920 with his friend Jean Barré (1880-1967), he published a major work titled Travaux neurologiques de guerre, a book that described the two doctors clinical experiences during wartime. He was a member of French, American and Japanese academies of science, and in 1949 was appointed commander of the Légion d'honneur. He died in Paris.
His daughter, Andrée, married the aircraft manufacturer, Claude de Cambronne.
- Guillain-Laroche-Léchelle reaction, Réaction au benjoin colloidal.
- Guillain–Barré–Strohl syndrome, the most common form of acquired inflammatory polyneuropathy.
- Guillain-Thaon syndrome, syndrome rare due to syphilis of the central nervous system.
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