AZO/Cu/AZO/SiO₂ films were sputtered on glass substrates at room temperature. Effects of SiO₂ layer on structure, conductivity and solar control performance of AZO/Cu/AZO/SiO₂ films were investigated. The SiO₂ layer is useful to the growth of AZO grains in the top layer, improvement of conductivity and blue shift of transmission spectrum. With the increase of SiO₂ layer thickness, the sheet resistance decreases first and then increases, band gap increases and near-infrared barrier rate first increase significantly and then decrease slightly. When the SiO₂ layer thickness is 36 nm, the multilayer film possesses lowest sheet resistance of 8.73 Ohm/square, the lowest infrared emissivity of 8–14 μm is 0.048, highest near-infrared barrier rate of 60% and high transmittance of 81.2%. Both the change of conductivity and the increase of band gap make the ability of multilayer film to block near-infrared light improve significantly.