A block copolymer containing an azobenzene (Az) moiety in the side chain was prepared by atom transfer radical polymerization (ATRP). For comparison, a random copolymer with a similar Az content was also designed. Their photoresponsive and holographic behavior was investigated in thin films. The block copolymer film showed microphase separation with cylinder microdomains after annealing, which was then irradiated at 366 nm. It was found that trans-cis photoisomerization in the block copolymer film was slower than that in the random copolymer film. This may be due to the restricted motion of the Az moieties in the Az blocks. The photoinduced birefringence (Delta n) of the block copolymer film was higher than that of the random copolymer film upon irradiation with a linearly polarized beam. In holographic recording, similar results were obtained. A block copolymer with 22-mol% Az showed a liquid-crystalline (LC) phase, while a random copolymer with 24-mol% Az exhibited no LC phase. The block copolymer showed an LC phase at a lower Az content compared with the random copolymer, suggesting that the molecular alignment of Az mesogenic groups is enhanced by cooperative motion of LCs in block copolymer films.