Novel Y-shaped amphiphilic block copolymers of poly(ethylene glycol) and poly(N-isopropylacrylamide), PEG-b-(PNIPAM)2, were successfully synthesized through atom transfer radical polymerization (ATRP). A difunctional macroinitiator was prepared by esterification of 2,2-dichloroacetyl chloride with poly(ethylene glycol) monomethyl ether (PEG). The copolymers were obtained via the ATRP of N-isopropylacrylamide (NIPAM) with CuCl/Me6TREN as catalyst and DMF/H2O (v/v = 3:1) mixture as solvent. The resulting polymers were characterized by gel permeation chromatography (GPC) and 1H NMR. These block copolymers show controllable molecular weights and narrow molecular weight distributions (PDI <1.15). Their phase transition temperatures and enthalpy changes in aqueous solution were measured by differential scanning calorimetry (DSC). The results indicate a significant influence of the macromolecular architecture on the phase transition. This is the first study into the effect of molecular architecture on the phase transition using Y-shaped amphiphilic block copolymer composed of PEG and PNIPAM.