The synthesis of di- and triblock copolymers, involving methyl methacrylate (MMA), butyl acrylate, and methyl acrylate, using copper-based atom transfer radical polymerization (ATRP) is reported. It was found that poly(MMA) macroinitiator is able to initiate the ATRP of acrylic monomers. However, for polyacrylates to effectively initiate the ATRP of MMA, the end group should be a bromine atom and the catalyst CuCl; that is, halogen exchange should take place. ABA-type triblock copolymers, where B poly(butyl acrylate) and A = poly(methyl methacrylate), were synthesized by growing the center block first using a difunctional initiator and then adding MMA to the ends.