Laminated and blending composites are designed to study the interfacial effects on the overall conductivity based on materials with different conductive mechanisms. The blends exhibit porous morphology because of the phase separation among the components, providing lager contacting areas between polymer chains and ions, and also more moving spaces for them, and hence their conductivity increases with the addition of polyaniline (PAN) to a maximum value of 0.075Scm(-1) at 75% PAN of polyvinyl butyral (PVB) (wt.%). The laminated films also show conductivity improvement, but inferior to that of blends from room temperature to 60 degrees C. The element parameters of the interfaces have great effects on their conductive performances as tested by the electrode/solid polymer electrolytes (SPE)/electrode model. The values of the electrode/SPEs interface are in the same magnification, while the value between PAN and PVB/polyethylene glycol(400)/LiClO4 layers is much bigger than those of the electrode/SPEs, providing the fact that the interface effect between different materials (metal/polymer, polymer/polymer) plays a vital role in determining their overall conductive performances.