A novel six-arm star block copolymer comprising polystyrene (PS) linked to the center and p-conjugated poly (3-hexylthiophene) (P3HT) was successfully synthesized using a combination of atom transfer radical polymerization (ATRP) and click reaction. First, star-shaped PS with six arms was prepared via ATRP of styrene with the discotic six-functional initiator, 2,3,6,7,10,11-hexakis(2-bromoisobutyryloxy)triphenylene. Next, the terminal bromides of the star-shaped PS were substituted with azide groups. Afterward, the six-arm star block copolymer PS-b-P3HT was prepared using the click coupling reaction of azide-terminated star-shaped PS with alkynyl-terminated P3HT. Various techniques including 1H NMR, Fourier-transform infrared and size-exclusion chromatography were applied to characterize the chemical structures of the intermediates and the target block copolymers. Their thermal behaviors and optical properties were investigated using differential scanning calorimetry and UVvis spectroscopy. Moreover, atomic force microscopy (AFM) was utilized to observe the morphology of the star block copolymer films. In comparison with two linear diblock copolymer counterparts, AFM results reveal the effect of the star block copolymer architecture on the microphase separation-induced morphology in thin films. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012