The emergence of photoinduced energy/electron transfer-reversible addition-fragmentation chain transfer polymerization (PET-RAFT) not only revolutionized the field of photopolymerization but also accelerated the development of porphyrin-based photocatalysts and their analogues. The continual expansion of the monomer family compatible with PET-RAFT polymerization enhances the range of light radiation that can be harnessed, providing increased flexibility in polymerization processes. Furthermore, the versatility of PET-RAFT polymerization extends beyond its inherent capabilities, enabling its integration with various technologies in diverse fields. This integration holds considerable promise for the advancement of biomaterials with satisfactory bioapplications. As researchers delve deeper into the possibilities afforded by PET-RAFT polymerization, the collaborative efforts of individuals from diverse disciplines will prove invaluable in unleashing its full potential. This Review presents a concise introduction to the fundamental principles of PET-RAFT, outlines the progress in photocatalyst development, highlights its primary applications, and offers insights for future advancements in this technique, paving the way for exciting innovations and applications.