α-Amino acids are vital structural motifs in both bioactive compounds and synthetic building blocks. However, the photocatalytic synthesis of α-amino acids directly from C(sp3)-H bonds and CO2 is a long-standing challenge. Here we report a visible-light-driven C(sp3)-H bond carboxylation of benzylamine with CO2 to synthesize substituted arylglycines. This reaction has mild reaction conditions, good functional group tolerance, and a wide substrate scope. Mechanistic studies show that carbon radicals and carbon anions as the key intermediates may be generated through a consecutive photoinduced electron transfer process.