The well-defined photoresponsive polymethacrylate containing azo chromophore, poly{1‘-octyloxy-4‘-(6-methacryloxy)hexyloxy-5‘-phenylmethaneone-(2-phenyl)azobenzene (AHMA)} (PAHMA), was prepared via reversible addition−fragmentation chain transfer (RAFT) polymerization in anisole solution using 2-cyanoprop-2-yl 1-dithionaphthalate (CPDN) as the RAFT agent and 2,2‘-azobis(isobutyronitrile) (AIBN) as an initiator. The kinetic plots of polymerization were first-order and the molecular weights (Mn(GPC)s) of the homopolymer (PAHMA) with relatively low polydispersity index values (PDIs ≤ 1.37) increased with monomer conversions throughout the polymerization processes. Furthermore, the kinetic plots of chain extension with both methyl methacrylate (MMA) and styrene (St) using the obtained PAHMA as a macro-RAFT agent were also first-order. The Mn(GPC)s of the diblock copolymers, PAHMA-b-PMMA and PAHMA-b-PS, increased with the respective monomer conversions. These results indicated that most of the PAHMA chains were still “living”. The structure and properties of the polymers were characterized by 1H NMR, GPC, and UV−vis spectra. The photoisomerization of the polymer was examined. On irradiation with a linearly polarized Kr+ laser beam, the birefringence was induced in the polymer films to the level of 0.075. With illumination of linearly polarized Kr+ laser beam at modest intensities (120 mW/cm2), significant surface relief gratings (SRGs) formed on the polymer films were observed.