The pH-responsive amphiphilic PCL-b-PAA was synthesized via ATRP of Methoxymethlacrylate (MOMA), a hemiketal ester of acrylic acid, with PCL-Br as macroinitiator, and followed by the hydrolysis of PMOMA segment under a mild condition without the degradability of PCL segment. 1H NMR, GPC,and FTIR were used to characterize the structure of polymers. Subsequently,the self-assembly of PCL-b-PAA was investigated by ?uorescence spectroscopy, DLS and TEM. The amphiphilic block copolymer formed the core-shell structural spherical micelles with 70 nm and the hydrodynamic radiusvaried with pH value and ionic strength. The MTT assay indicated that PCL-b-PAA was low toxic to fibroblast cells.