Airi Yamaguchi, Tomoko Yajima
Abstract Hydroxyperfluoroalkylation of styrenes is a powerful transformation that enables the simultaneous introduction of hydroxy and perfluoroalkyl groups with considerable implications in pharmaceuticals and materials science. In the past 5 yr, metal-free and visible-light-mediated strategies have emerged, including organic dyes, strongly reducing photocatalysts, electron donor–acceptor complexes, halogen-bonding systems, and confined polymeric nanoreactors. This review highlights recent advances, mechanistic insights, and future directions toward sustainable, scalable, and broadly applicable hydroxyperfluoroalkylation reactions.