In 1689, he wrote a paper on algebra, which contains the theorem on the position of the roots of an equation. In 1675, he relocated to Paris and worked as an arithmetical expert. Rolle primarily worked on Diophantine analysis, algebra, and geometry. In 1685, he was elected to the Royal Academy of the Sciences. In 1691, Rolle published "Rolle's Theorem", for which he is best remembered. His theorem, which is a specialized case of the Mean Value Theorem, guaranteed the existance of a horizontal tangent line (f'(x)=0) between points a and b given that f(a) = f(b) = 0.

Rolle also gained some notariety by solving a problem posed by Jacques Ozanam in 1682. Impressed by Rolle's achievement, Jean-Baptiste Colbert, controller general of finance under King Louis XIV of France, rewarded Rolle with a pension for his diligent work.