Novel and well-defined amphiphilic H-shaped terpolymers poly(L-lactide)-block-(poly(2-(N,N-dimethylamino) ethyl methacrylate)-block-)poly(epsilon-caprolactone)(-block-poly(2-(N,N-dimethylamino) ethylmethacrylate))-b-poly(L-lactide) (PLLA-b-(PDMAEMA-b-)PCL(-b-PDMAEMA)-b-PLLA) were synthesized by the combination of ring-opening polymerization, atom transfer radical polymerization, and click chemistry. The H-shaped amphiphilic terpolymers can self-assemble into spherical nano-micelles in water. Because of the dually responsive (temperature and pH) properties of PDMAEMA segments, the hydrodynamic radius of the micelles of the H-shaped terpolymer solution can be adjusted by altering the environmental temperature or pH values. The thermal properties investigation and the crystalline morphology analysis indicate that the branched structure of the H-shaped terpolymers and the presence of amorphous PDMAEMA segments together led to the obvious decrease of PCL segments and the complete destruction of crystallinity of the PLLA segments in the H-shaped terpolymers. In addition, the H-shaped terpolymer film has better hydrophilicity than linear PCL or triblock polymer of PLLA-b-(N-3-)PCL(-N-3)-b-PLLA, due to the decrease or destruction of the crystallizability of the PCL or PLLA in the H-shaped terpolymer and the presence of hydrophilic PDMAEMA segments. These unique H-shaped amphiphilic terpolymers composed of biodegradable and biocompatible PCL and PLLA components and intelligent and biocompatible PDMAEMA component will have the potential applications in biomedical fields. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 50: 2541-2552, 2012