The work aims to prepare a new type of green TiO2/PVB-PANI/PVB hybrid coating to study the anti-corrosion mechanism of hybrid coating on stainless steel in NaCl solution. Polyaniline (PANI) was synthesized by in-situ chemical oxidation. PVB was used as binder and methanol was used as solvent. The TiO2/PVB-PANI/PVB hybrid coating was prepared on the surface of stainless steel by dip-coating method and knife coating method. Functional groups, light absorption properties, structure and microstructures were analyzed by Fourier transform infrared (FT-IR), UV-vis diffuser reflectance (UV-Vis DRS), X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS). The anti-corrosion mechanism and corrosion resistance of TiO2/PVB-PANI/PVB hybrid coating and PANI/PVB coating were compared and analyzed by electrochemical method and scratch immersion test. The photoresponse current of TiO2/PVB-PANI/PVB hybrid coating was 250 nA/cm2, and its photovoltage decreases by 0.12 V compared with stainless steel. From the electrochemical tests, compared with stainless steel, the self-corrosion potential of the TiO2/PVB-PANI/PVB hybrid coating rose, the self-corrosion current density decreased and the radius of the capacitive anti-arc increased. The electrochemical reaction rate at the interface obviously increased during illumination. The scratch immersion test showed that the corrosion resistance of the TiO2/PVB-PANI/PVB hybrid coating was better than that of the PANI/PVB coating in the presence or absence of light. The contrast between the two coatings in the light was more obvious. TiO2/PVB-PANI/PVB hybrid coating provided excellent corrosion protection for stainless steel by virtue of physical shielding, anti-corrosion of PANI and photocathodic protection.