Modern photocatalysis has proven its generality for the development and functionalization of native functionalities. To date, the field has found broad applications in diverse research areas, including the total synthesis of natural products. This contribution covers recent reports of total syntheses involving as a key step a photocatalytic reaction. Among the selected examples, the photocatalytic processes proceed in a highly chemo-, regio-, and stereoselective manner, thereby allowing the rapid access to structurally complex architectures under light-driven conditions.