A NiP/TiO2 composite film on carbon steel was prepared by electroless plating and sol-gel composite process. An artificial neural network was applied to optimize the prepared condition of the composite film. Corrosion behavior of the NiP/TiO2 composite film was investigated by polarization resistance measurement, anode polarization, ESEM (environmental scanning electron microscopy)and EIS (electrochemical impedance spectroscopy) measurements. Results showed that the NiP/TiO2 composite film has a good corrosion resistance in 0.5mol/L H2SO4 solution. The element valence of the composite film was characterized by XPS (X-ray photoelectron spectroscopy) spectrum, and an anticorrosion mechanism of the composite film was discussed.