Polystyrene (PS)-incorporated polyhedral oligomeric silsesquioxanes (POSS) organicinorganic hybrid graft copolymer could be achieved by click coupling reaction between alkyne groups in POSS and azido groups in PS via graft onto strategy. Alkyne-functionalized POSS was synthesized via thiol-ene facile click reaction and subsequent amidation reaction with very high yield. Azido-multifunctionalized PS could be synthesized by chloromethylation and subsequent azido reaction. The chemical structures of PS-(CH2Cl)m, PS-(CH2N3)m, and PS-g-POSS were determined by Fourier transform infrared and 1H NMR characterization. PS-g-POSS presented a better hydrophobic property with contact angle of 113 degrees than that of PS (85 degrees). And PS-g-POSS with 5% of grafting degree had lower glass transition temperature (Tg) than that of PS and then it increased up to 112 degrees C with grafting degree. An obvious aggregation of POSS phase with 1080 nm in size was formed in PS-g-POSS matrix. In addition, 5 wt % of PS-g-POSS was added to general purpose polystyrene (GPPS) to remarkably improve its tensile strength from 45 to 57 MPa. (c) 2012 Wiley Periodicals, Inc.