The synthesis of di- and triblock copolymers using atom transfer radical polymerization (ATRP) of n-butyl acrylate (BA) and methyl methacrylate (MMA) is reported. In particular, synthetic procedures that allow for an easy and convenient synthesis of such block copolymers were developed by using CuBr and CuCl salts complexed with linear amines. Polymerizations were successfully conducted where the monomers were added to the reactor in a sequential manner. Poor cross-propagation between poly(n-butyl acrylate) (PBA) macroinitiators and MMA was minimized, and therefore control of molecular weights and distributions was realized, by using halogen exchange-a technique involving the addition of CuCl to the MMA during the chain extension of the PEA macroinitiator. High molecular weight (M-n similar to 90,000) and low polydispersity (M-w/M-n < 1.35) ABA triblock copolymers were also prepared and their structure and properties in bulk have been preliminary characterized indicating the potential of ATRP for the production of all-acrylic thermoplastic elastomers.