The surface structures of polypyrrole/silicon crosslinked poly( styrene/butyl acrylate/hydroxyethyl acrylate) (PSBH) conductive composite films were investigated by X-ray photoelectron spectroscopy and scanning electron microscopy. It was found that the conductive composite films were of a "sandwich" structure, and the surfaces greatly differ in chemical compositions and phase morphologies from the bulk. The Si and N contents exhibit opposite gradient change with the measured depth of the two surface layers in the composite films, namely, the decrease in Si content and the increase in N content with increase in the depth of the surface layers. However, the Ndelta+/N ratios in polypyrrole decreased with the measured depth of the conductive composite film. It was also found that the conductive composite film based on silicon crosslinked matrix exhibits more environmental stable than that based on linear matrix.