We have fabricated polymer/polymer blend solar cells consisting of poly(3-hexylthiophene) as the electron donor and poly{2,7-(9,9-didodecylfluorene)-alt-5,5-[4',7'-bis(2-thienyl)-2',1',3'-benzothiadiazole]} as the acceptor. The power conversion efficiency (PCE) was strongly dependent on solvents employed for spin coating. The best PCE of 2.0% was obtained for thermally annealed devices prepared from a chloroform solution, in contrast to devices fabricated from chlorobenzene and o-dichlorobenzene solutions. On the basis of the morphology-performance relationship in the polymer blends examined by atomic force microscopy and the photoluminescence quenching measurements, we conclude that the highly efficient performance is achieved by thermal purification of nanoscale-phase-separated domains formed by spin coating from chloroform.