A technique is described for the synthesis of polystyrene-block-poly (vinylidene fluoride)-block-polystyrene (St-VDF-St) triblock copolymers through a poly(vinylidene fluoride) macroinitiator. The bromine terminated poly(vinylidene fluoride), which was prepared by radical telomerization of vinylidene fluoride with 1,2-dibromotetrafluoroethane, initiated polymerization of styrene in presence of copper(I) bromide and alpha ＇alpha-bispyridine complexes. It was found that molecular weights increased linearly in styrene conversion and polydispersities were low. The macroinitiator and block copolymers were characterized by g.p.c. and n.m.r.