An all electrochemical deposition process was developed to prepare the polypyrrole nanocomposite films containing multiple layers of CdSe and CdTe. The CdSe layer grew on top of polypyrrole in a Volmer-Weber mode leading to an increase in surface roughness, while the subsequent CdTe layer filled up the interisland space of the CdSe layer resulting in smoother surfaces. A complete coverage of CdTe over the CdSe layer significantly improved the photoluminescence performance of the composite film. This demonstrates that wider band gap materials (CdSe here) can be enhanced in photoluminescence performance with passivation of surface states offered by a narrower band gap material (CdTe here) provided that the lowest conduction band of the narrower band gap material is located higher in energy level than that of the wider band gap material. A top covering layer of polypyrrole not only further smoothed the surface but also further boosted the photoluminescence intensity of the nanocomposite film because of the enhanced radiative electron-hole recombination.