Fluoropolymers have found broad applications for many decades. Considerable efforts have focused on expanding access toward main-chain fluorinated polymers. In contrast to previous polymerizations of gaseous fluoroethylenes conducted at elevated temperatures and with high-pressure metallic vessels, we here report the development of a photoorganocatalyzed reversibledeactivation radical alternating copolymerization of chlorotrifluoroethylene (CTFE) and vinyl ethers (VEs) at room temperature and ambient pressure by exposing to LED light irradiation. This method enables the synthesis of various fluorinated alternating copolymers with low D and high chain-end fidelity, allowing an iterative switch of the copolymerization between "ON" and "OFF" states, the preparation of fluorinated block alternating copolymers, as well as postsynthetic modifications.