We successfully fabricated polymer photovoltaic cells with bilayer structure of distinct tetrahydrofuran (THF)-soluble polymers by Evaporative Spray Deposition using Ultradilute Solution (ESDUS). The top layer of an acceptor polymer was deposited by ESDUS onto a bottom layer consisting of donor polymers (polythiophene, polyphenylenevinylene or polyfluorene). PL spectra of the bilayer cells indicated that the top layer can be formed without dissolving the bottom layer. The photovoltaic performance was improved compared with the blend cells of the donor polymer and the acceptor polymer prepared by conventional spin-coating technique. It is suggested that layered structure of a donor polymer and an acceptor polymer is more suitable for polymer photovoltaics than the blend.