Ultrathin films of poly(p-phenylenevinylene) (PPV) were fabricated by the layer-by-layer (LbL) deposition technique with a cationic PPV precursor and an anionic PPV. The hole mobility of the PPV-based LbL film was as high as 4 x 10(-4) cm(2) V(-1) S(-1). Multilayered polymer solar cells with the PPV-based LbL film as a light-harvesting layer were fabricated by a combination of the spincoating and the LbL deposition technique, exhibiting a power conversion efficiency of 0.28% under AM1.5G simulated solar illumination with 100 mW cm(-2). The high performance is ascribed to the high light-harvesting efficiency and hole mobility of the PPV-based LbL layer. (C) 2008 Elsevier B.V. All rights reserved.