A novel ABA-type triblock copolymer, where A and B correspond to azobenzene (Az) containing polymethacrylate and poly(ethylene oxide) (PEO), respectively, was synthesized by atom transfer radical polymerization. Langmuir-Blodgett monolayers showed characteristic microphase separation structures depending on the isomerization state of the Az unit. The trans-to-cis isomerization induced an anisotropic elongation of the domain of the Az polymer parallel to the rod maintaining the width. Thus, successful photocontrol of nanostructures formed by the block copolymer in the two dimensions was performed. A plausible model for the Az packing and PEO conformation is proposed.