The past two decades have witnessed the significant progress of regulated reversible addition–fragmentation chain transfer (RAFT) polymerization, and different strategies, especially those with light, were designed, such as direct photoexcitation of RAFT agents, using photoinitiators and recyclable/degradable photocatalysts. More recently, photosensitive azobenzenes as external photoadditives have also been utilized to switch on/off the RAFT polymerization, in which photoelectron transfer (PET) between free radicals and azobenzenes was involved. This minireview summarizes these recently developed techniques for photoregulated RAFT polymerization and their possible applications.