A novel synthetic route, combining three reversible addition-fragmentation chain transfer (RAFT) and one atom transfer radical polymerization (ATRP) processes, for the preparation of a miktoarm dumbbell-like amphiphilic triblock copolymer, poly(poly(ethylene glycol) methyl ether methacrylate)-b-polystyrene-b-(poly(4-vinylbenzyl chloride)-g-polystyrene) (PPEGMA-b-PS-b-(PVBC-g-PS)), was developed using 2-cyanoprop-2-yl 1-dithionaphthalate (CPDN) as a RAFT agent, and the benzyl chloride group of the VBC units in the PVBC block as active ATRP macroinitiators, respectively. The structures of the obtained (co)polymers were characterized by H-1 NMR spectroscopy. The obtained PPEGMA-b-PS-b-(PVBC-g-PS) amphiphilic triblock graft copolymer could self-assemble into spherical micelles with 100-300 nm diameters in a selective solvent.