Organocatalysis, catalysis mediated by small chiral organic molecules, is a powerful technology for enantioselective synthesis, and has found extensive applications within traditional ionic, two-electron-pair reactivity domains. Recently, organocatalysis has been successfully combined with photochemical reactivity to unlock previously inaccessible reaction pathways, thereby creating new synthetic opportunities. Here, we critically describe the historical context, scientific reasons, and landmark discoveries that were essential to expanding the functions of organocatalysis to include one- electron-mediated chemistry and excited-state reactivity.