Cationic polymerization is an important branch of polymer chemistry. Traditional cationic polymerization must be carried out in anhydrous and low temperature environment, with harsh operating conditions, high operating costs and high energy consumption. Visible light induced cationic polymerization is simple, environmentally friendly, and low‐cost, so it has become a research hotspot of living cationic polymerization. This paper gives an overview of the recent advances (mainly from 2015 to 2023) on visible‐light‐induced cationic polymerization, with a focus on visible‐light‐initiated and visible‐light‐controlled cationic polymerization. On the basis of controlling cationic polymerization to achieve macromolecular reaction engineering, the realization of temporal scale control will be the main development direction in the future.

On the basis of synthesizing a highly efficient chain‐transfer agent ethyl (1‐isobutoxyethyl) carbonotrithioate(CTA), living cationic polymerization of isobutyl vinyl ether (IBVE) was successfully initiated by visible light catalysis. The random copolymerization of isobutyl vinyl ether and propyl vinyl ether (PVE), cyclohexyl vinyl ether (CyVE), and 2‐chloroethyl vinyl ether (CEVE) was achieved on the basis of investigating the reactivity ratios of vinyl ether monomers. The influence of photocatalyst (PC) concentration and wavelength on the copolymerizations was investigated. It was found that high PC concentration results in a fast polymerization rate. The wavelength of the blue LED was most suitable for this reaction system. This photocatalytic reaction provides a new way for molecular design of cationic polymerization.

Hydroxyl-terminated linear and star-shaped telechelic polyisobutylene have been successfully synthesized by living cationic polymerization using propylene oxide (PO)/Titanium tetrachloride (TiCl4) as the initiator system.