We developed a novel block copolymer composed of poly(ethylene oxide) (PEO) and polymethacrylate functionalized with liquid-cryst-alline oligothiophene by using the atom transfer radical polymerization (ATRP), aiming at application to organic photovoltaic (OPV) cells. Thermal investigation showed that the resultant polymer exhibits liquid-crystalline phases both on heating and cooling. Morphologies of the thin films of the block copolymer were investigated by atomic force microscopy (AFM). Microphase separation with a small size of almost 10nm (nano-phase-separated structures) was observed upon annealing.