A series of polystyrene-b-poly(dimethylsiloxane)-b-polystyrene (PS/PDMS/PS) triblock copolymers had been synthesized by atom transfer radical polymerization (ATRP). The products had been characterized by Fourier transform infrared, gel permeation chromatography, differential scanning calorimetry, thermogravimetric analysis, contact angle, and scanning electron microscope. The results indicate that the PS chains have been successfully blocked onto the PDMS back bone, and the PS-b-PDMS-b-PS triblock copolymers have low-surface tension, good thermal stability, and microphase separation configuration. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013