The Ti/Pt/Sb-SnO2 electrodes with nanoscale Pt interlayers were fabricated by pyrolytic coating combining with magnetron sputtering method. The effects of introducing Pt interlayer were evaluated by physicochemical and electrochemical measurements. We calculated the texture coefficients of SnO2 crystals growing on Ti and Ti/Pt substrates according to the XRD data, and found the SnO2 crystalline grains growing on Ti and Ti/Pt having the different preferred orientations. Hence, we used the first-principles method building three kinds of supercells along diverse preferred orientations (110), (101) and (211) to simulate three types SnO2 crystalline grains. The computation results indicated the conductivity of supercell built along the (101) face was better than that of (211) face supercell. Furthermore, electrochemical tests such as linear sweep voltammetry (LSV), chronopotentiometry and electrochemical impedance spectroscopy (EIS) had been carried out on the Ti/Pt/Sb-SnO2 electrodes. We also discussed the changes of oxygen evolution overpotential and charge transfer resistant on the Ti/Pt/Sb-SnO2 electrodes in a physical perspective.