Born in Limoges, Haute-Vienne, Chevalier studied at the École Polytechnique, obtaining an engineering degree at the Paris École des mines in 1829.

In 1830, after the July Revolution, he became a Saint-Simonian, and edited their paper Le Globe. The paper was banned in 1832, when the "Simonian sect" was found to be prejudicial to the social order, and Chevalier, as its editor, was sentenced to six months imprisonment.

After his release, Minister of the Interior Adolphe Thiers sent him on a mission to the United States and Mexico, to observe the state of industrial and financial affairs in the Americas. In Mexico he exchanged ideas with the mineralogist and politician Andrés Manuel del Río. It was during this trip that he also developed the idea that the Spanish-speaking and Portuguese-speaking parts of the Americas shared a cultural or racial affinity with all the European peoples with a Romance culture. Chevalier postulated that this part of the Americas were inhabited by people of a "Latin race," which could be a natural ally of "Latin Europe" in its struggle with "Teutonic Europe," "Anglo-Saxon America" and "Slavic Europe." The idea was later taken up by French and Latin American intellectuals and political leaders of the mid- and late-nineteenth century, who no longer looked to Spain or Portugal as cultural models, but rather to France, and who coined the term "Latin America."

In 1837 he wrote a well received work, Des intérèts matériels en France, after which his career took off. At age 35, he was appointed professor of political economy at the Collège de France. He was elected a député for the département of Aveyron in 1845, an appointment of Senator followed in 1860. In 1859, he was elected a foreign member of the Royal Swedish Academy of Sciences.

Together with Richard Cobden and John Bright he prepared the free trade agreement of 1860 between the United Kingdom and France, which is still called Cobden-Chevalier Treaty.

He died in Montpellier.