In this work, we report a much simpler and low-cost method to prepare main-chain-type semifluorinated alternating copolymers by the formation of a halogen bond (XB) complex between α,ω-diiodoperfluoroalkanes and amines/halide salts. It is interesting that the terminal iodine functional group of the polymer chains is easily lost in the amine-promoted system, while the loss can be significantly reduced by adding a small amount of water. Importantly, the system promoted by halide salts can ensure complete retention of the iodine functional group. Overall, the establishment of this method provides a new strategy for designing smart fluoropolymer materials in a green and environmentally friendly facile manner under irradiation with visible light at room temperature.