The electrochromic behavior of polyaniline poly(vinyl alcohol) composite films (CPAn-PVA) combined with electrochemically synthesized Prussian blue films (PB) was investigated in LiClO4-CH3CN nonaqueous aprotic solution. The combination was achieved by chemical deposition of CPAn-PVA on PB. When the combined films (CPAn-PVA-PB) are prepared with the appropriately low quantity of PB, CPAn-PVA-PB showed various visible absorption spectra overlapped roughly with the absorption of the component materials at different applied potentials. CPAn-PVA-PB provided the color change from green to blue at much lower applied potential than did CPAn-PVA. However, the combined PB eliminates protons from the first oxidized polyaniline chains to decrease the electrochemical activity of polyaniline. Therefore, to construct multicolor electrochromic devices by the combination of polvaniline with the other electrochromic materials, it is necessary to select the materials containing no deprotonation activity.