In the past decade, photochemistry has emerged as a growing area in organic and polymer chemistry. Use of light to drive polymerization has advantages by imparting spatial and temporal control over the reaction. Photoinduced electron/energy transfer reversible addition-fragmentation chain transfer polymerization (PET-RAFT) has emerged as an excellent technique for developing well-defined polymers from a variety of functional monomers. However, the mechanism, of electron versus energy transfer is debated in the literature, with conflicting reports on the underlying process. This perspective focuses on the mechanistic aspects of PET-RAFT, in particular, the electron versus energy transfer pathways. The different mechanisms are evaluated, including evidence for one versus the other mechanisms. The current literature has not reached a consensus across all PET-RAFT processes, but rather, each catalytic system has unique characteristics.