The synthesis of block copolymers comprising fluoropolymer and non-fluoropolymer segments is reported. The synthetic method is based on chain transfer emulsion polymerization of fluoromonomers and their subsequent employment as macroinitiators in atom transfer radical polymerization (ATRP) of non-fluorinated vinyl monomers. Trichloromethyl-terminated copolymers of vinylidene difluoride (VDF) and hexafluoropropylene (HFP), possessing molecular weights up to 25 000 g/mol, were obtained by emulsion polymerization in the presence of chloroform and used to initiate the ATRP of styrene (St) and methyl methacrylate (MMA) to form a series of P(VDF-co-HFP)-b-PS and P(VDF-co-HFP)-b-PMMA block copolymers. NMR, GPC, DSC, and TEM analysis confirmed the compositions of the block copolymers. The polymers exhibited a phase-separated morphology in the solid state and possessed distinct glass transition temperatures associated with fluoropolymer, PS, and PMMA domains.