A thin film of bis-amino silane of bis-[triethoxysilylpropyl]amine (BTSPA) was coated on carbon steel surface by electrodeposition and then chemically modified by adsorption of CeO2 nanoparticles. The composition and structure of BTSPA/CeO2 composite film were characterized by electron microprobe analysis, X-ray photoelectron spectroscopy and infrared reflection absorption spectroscopy, while the anti-corrosion performance of the composite film on carbon steel was investigated using electrochemical impedance spectroscopy and scanning reference electrode technique. The results demonstrated that the BTSPA/CeO2 composite film formed on the BTSPA film electrodeposited at −0.8V vs. SCE, which exhibited an enhanced corrosion protection for carbon steel and an improvement of adhesion between substrate and outer coating. The CeO2 nanoparticles incorporated/absorbed into the SiOSi network of the BTSPA film were able to promote the condensation of hydrolysis product SiOH groups to the SiOSi network on the surface and to provide a barrier and corrosion inhibition properties for carbon steel, which is beneficial for improvement of the corrosion protection of the composite film for carbon steel.