The grafting polymerization of styrene initiated by the alkyl chloride groups of poly(CTFE alt VE) and poly[(CTFE aft VE) co (HFP alt VE] copolymers (where CTFE HFP and VE stand for chlorotrifluoroethylene (CTFE) hexafluoropropylene (HFP) and vinyl ether (VE) respectively) followed by the chemical modification of the polystyrene grafts are presented First the fluorinated alternating copolymers were produced by radical copolymerization of CTFE (with HFP) and VE Second atom transfer radical polymerization enabled the grafting polymerizetion of styrene in the presence of the poly(CTFE alt VE) macroinitiator using the alkyl chloride group of CTFE as the initiation site Kinetics of the styrene polymerization indicated that such a grafting had a certain controlled character For the first time grafting of polystyrene onto alternating fluorinated copolymers has been achieved Differential scanning calorimetry thermo grams of these graft copolymers exhibited two glass transition temperatures assigned to both amorphous domains of the polymeric fluorobackbone (ranging from 20 to +56 degrees C) and the polystyrene grafts (ca 95 degrees C) The thermostability of these copolymers increased on grafting Thermal degradation tern peratures at 5% weight loss were ranging from 193 to 305 degrees C when the polystyrene content varied from 81 to 27% Third chloromethylation of the polystyrene grafts followed by the cat ionization of the chloromethyl dangling groups led to original ammonium containing graft copolymers (c) 2010 Wiley Penodi cals Inc J Polym Sci Part A Polym Chem 48 5801-5811 2010