Multilayered polymer thin-film solar cells have been fabricated by wet processes such as spin-coating and layer-by-layer deposition. Hole- and electron-transporting layers were prepared by spin-coating with poly(3,4-ethylenedioxythiophene) oxidized with poly(4-styrenesulfonate) (PEDOT:PSS) and fullerene (C60), respectively. The light-harvesting layer of poly-(p-phenylenevinylene) (PPV) was fabricated by layer-by-layer deposition of the PPV precursor cation and poly(sodium 4-styrenesulfonate) (PSS). The layer-by-layer technique enables us to control the layer thickness with nanometer precision and select the interfacial material at the donor–acceptor heterojunction. Optimizing the layered nanostructures, we obtained the best-performance device with a triple-layered structure of PEDOT:PSS|PPV|C60, where the thickness of the PPV layer was 11 nm, comparable to the diffusion length of the PPV singlet exciton. The external quantum efficiency spectrum was maximum (ca. 20%) around the absorption peak of PPV and the internal quantum efficiency was estimated to be as high as ca. 50% from a saturated photocurrent at a reverse bias of −3 V. The power conversion efficiency of the triple-layer solar cell was 0.26% under AM1.5G simulated solar illumination with 100 mW cm−2 in air.