Radical copolymerizations of chlorotrifluoroethylene (CTFE) with vinyl ethers such as 2-chloroethyl vinyl ether (CEVE) and ethyl vinyl ether (EVE) were performed at 75 °C in the presence of peroxide initiator. Three copolymers were obtained and characterized by means of both NMR and elemental analysis. Then, the chlorine atoms in the side chains were converted into iodine atoms by nucleophilic substitution, which was monitored by 1 H NMR spectroscopy. A series of five copolymers with different amounts of iodine atoms in the side chains were thus obtained. These copolymers exhibited molecular weight values of about 25,000 g.mol-1, and the thermal analysis of the copolymers showed a starting degradation from about 220 °C. The Tg values were in the range of 34 to 41 °C and showed a linear dependance versus the content of iodine atoms.