This book presents recent reports of total syntheses involving a phoatalytic reaction as a key step in the methodology. Modern phoatalysis 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. Among the selected examples presented in this book, it highlights how the phoatalytic process proceeds in a highly chemo-, regio-, and stereoselective manner, thereby allowing the rapid access to structurally complex architectures under light-driven conditions.