We report a simple procedure for rapid, visible light-mediated, controlled radical polymerization in aqueous solutions. Based on the photoelectron transfer reversible addition–fragmentation chain transfer (PET–RAFT) polymerization, fast chain propagation at room temperature in water was achieved in the presence of reductant and without prior deoxygenation. A systematic study correlating irradiation intensity and polymerization kinetics, enabled by in situ nuclear magnetic resonance spectroscopy, provided optimized reaction conditions. The versatility of this procedure was demonstrated through a rapid triblock copolymer synthesis, and incorporation of water-labile activated esters for direct conjugation of hydrophilic small molecules and proteins. In addition, this technique boasts excellent temporal control and provides a wide range of macromolecular materials with controlled molecular weights and narrow molecular weight distributions.