Guillemain is thought to have been born in Paris, was brought up by the Count de Rochechouart, and started studying violin at an early age.
At the age of 24, Guillemain was working in Lyons, where he quickly established himself as one of the most sought-after performers, and was appointed first violinist of the Acadèmie de Musique.
His career was progressing rapidly, and by the early 1740s the composer was among the highest-paid musicians at the court, regularly performing in private concerts before the royal couple.
Fellow composer Louis-Claude Daquin praised Guillemain in his 1752 Lettre sur les hommes célèbres: When one speaks of a man full of fire, genius and life, one has to think of Monsieur Guillemain, Musician to the King; he is perhaps the most extraordinary and adroit violinist one can hear play.
He died in Chaville, then a small settlement near Paris, in 1770; some contemporary accounts describe his death as a bloody suicide, with the composer stabbing himself with a knife fourteen times.