The effect of the TiO 2 surface property on the conductivity of TiO 2 /antimony-doped tin oxide (ATO) has been revealed by the substrate modification with SiO 2 and ZrO 2. Their morphology, structural, and electric characteristics were investigated through field emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and electrochemical impedance spectra. The surface character of the raw and modified TiO 2 particles in water was investigated. The results indicated that the negatively charged substrate (−29.7 mV) was formed through the incorporation of SiO 2 coating, which facilitated the uniform deposition of positively charged ATO precursors further significantly improved the conductivity of TiO 2 /ATO composite. Conversely, the conductivity of TiO 2 /ZrO 2-ATO composite decreased due to the increase of electrostatic repulsion from the positively charged surface (+55.3 mV) of the substrate. The results confirmed the feasibility of the method proposed in this work.