This work focuses on studying a novel polymer/nanocrystal multilayer for the fabrication of donor and accepter typed photovoltaic device. Highly luminescent anionic CdTe nanocrystals were prepared by aqueous synthesis method using 3-mercaptopropionic acid as stabilizer. The resultant CdTe served as electron acceptor and poly(p-phenylene vinylene) (PPV) was used as electron donor. Through the electrostatic interactions between cationic PPV precursor poly(p-xylene tetrahydrothiophenium chloride) and anionic poly(sodium4-styrenesulfonate) (PSS), PPV/PSS complex was fabricated on the surface of pretreated quartz substrate by layer-by-layer electrostatic self-assembly method. UV-Vis spectrum shows that PSS in the PPV/PSS complex make PPV precursors thermally convert into PPV at a lower temperature and less time. PPV/ PSS/PPV/CdTe multilayer were fabricated on the surface of quartz substrate by electrostatic self-assembly method. The surface of the polymer/CdTe complex is flat, which was characterized by atomic force microscopy (AFM). UV-Vis spectrum of the polymer/CdTe complex shows that the absorbance increases with the increase of the number of deposition cycles. In the same way, PPV/PSS/PPV/CdTe multilayer were fabricated on the surface of ITO substrate disposed by the poly(3,4- ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS). The resultant polymer/ CdTe complex is measured under AM1.5G simulated solar illumination with 100mW•cm-2 in air. The open circuit current density (VOC) and short circuit current density (JSC) of the polymer/CdTe complex are 0.60 V and 0.305 mA•cm-2 which are better than PPV or CdTe nanocrystal individual. This could be ascribed to interfacial hole-electron converter between the conjugated polymer layer and CdTe nanocrystal layer. Besides, the photovoltaic properties of PPV/CdTe complex can be improved by controlling the layers of PPV/ CdTe nanocrystals complex on the ITO substrate.