The son of a wealthy shipowner from the West Indies island of St. Thomas, Deville studied medicine in Paris but became interested in chemistry by attending Louis Thenard's lectures. He isolated toluene and methyl benzoate from tolu balsam and investigated other natural products before turning to inorganic chemistry, following his appointment as professor of chemistry at Besançon (1845).

Deville's first major discovery was that of nitrogen pentoxide (1849). Following this success he became professor of chemistry at the Ecole Normale Supérieure (1851) and also lectured at the Sorbonne from 1853. Deville is best known for his work on the large-scale production of aluminum. This had been obtained by Kaspar Wöhler in 1827 but had been produced only in small quantities. Deville developed a commercially successful process involving reduction of aluminum chloride by sodium; the first ingot was produced in 1855. Deville was an expert on the purification of metals and produced (among others) crystalline silicon (1854) and boron (1856), pure magnesium (1857), and pure titanium (1857; with Wöhler). He did much work on the purification of platinum and in 1872 was commissioned to produce the standard kilogram.

After his work on aluminum, Deville's most important researches were those on dissociation. Working with L. J. Troost, he discovered that many molecules were dissociated at high temperature, giving rise to anomalous vapor-density results. Deville's work explained these results and helped to confirm Amedeo Avogadro's hypothesis. His other work included the production of artificial gemstones and improved furnaces.