Azobenzene-functionalized star polymers were synthesized by reversible addition fragmentation chain transfer (RAFT) polymerization. First, azobenzene-functionalized linear macro chain transfer agents (Macro-CTA) were synthesized by RAFT polymerization of 6-[4-(4'-Methoxyphenylazo)phenoxy]hexylmethacrylate (MAz6Mc) using 2-(2'-cyanopropyl)dithiobenzoate (CPDB) as RAFT agent in presence of AIBN as initiator in anisole. Subsequently, star azopolymers were synthesized by polymerization of a difunctional azomonomer, BMA2Az, with resultant Macro-CTA in presence of AIBN as initiator in anisole. Star azopolymers were characterized by GPC and spectroscopic methods. Thermal properties of star azopolymers were determined by DSC and TMA. Molecular weight versus conversion and molecular weight versus polymerization time attest to living polymerization characteristics. Photoisomerization behaviors of star azopolymers were studied by irradiation of both UV and visible light. Surface relief gratings were inscribed on star azopolymer films upon exposure to an interference pattern of (RCP + RCP) Ar(+) laser. A diffraction efficiency of 20% was obtained by exposure of Star-8 K(2.6 K) polymer film to an (RCP + RCP) Ar(+) laser for about 30 min. Surface relief grating structures were investigated by AFM and polarized optical microscopy. (C) 2011 Elsevier Ltd. All rights reserved.