A novel optically active monomer, 6-{4-[4-(1-phenyl-1H-tetrazol-5-yloxy)phenylazo] -phenoxy}-hexyl methacrylate (PTPPHMA) bearing tetrazole and azobenzol moieties, was synthesized and polymerized by reversible addition-fragmentation chain transfer (RAFT) polymerization using 2-cyanoprop-2-yl dithiobenzoate (CPDB) as the RAFT agent and 2, 2'-azobis(isobutyronitrile) (AIBN) as the initiator. Well-defined optically active photochromic polyPTPPHMA(P]PTPPHMA) was obtained. "Living"/controlled characteristics were observed in the polymerization: well-controlled molecular weights (M(n)s), narrow molecular weight distributions (M-w/M-n) of the polymers and successful chain-extension of PPTPPHMA with styrene (St) as the second monomer. The photochemical interconversion between trans and cis isomers of PPTPPHMA in N,N'-dimethyl formamide (DMF) solution was explored under irradiation of ultraviolet light. The photoinduced birefringence on the thin films of PPTPPHMA was investigated. A maximum birefringence of 0.1 was obtained, and no significant change of profiles of the birefringence after several cycles of writing/erasing/rewriting sequences was observed. The surface-relief-gratings (SRGs) were induced on the polymer films by interference of Kr+ laser beams at 413.1 nm with 35 mW/cm(2) intensity, the diffraction efficiencies from SRGs were measured to be in the range of 2.0-2.5%. The atomic force microscopy (AFM) results showed the gratings produced on the surfaces of the polymer film. (c) 2007 Wiley Periodicals, Inc.