A novel technique of selective SiO2formation called the interfacial oxidation method is proposed and proved feasible by experiment. By this technique, a poly‐Si/MoO2/Mo structure (poly‐Si on MoO2on Mo) can be converted to a poly‐Si/SiO2/Mo structure by annealing in an H2atmosphere so that SiO2is selectively formed on only Mo electrodes. The SiO2film formed by this method is shown to have almost the same properties as thermally grown SiO2film; the Si(2p) binding energy peak, etching rate for diluted HF(H2O:HF=100:3), and average breakdown strength were 102.9 eV, 102 Å/min, and 3.6×106V/cm, respectively. In addition, most diodes of 500×500  μm2area showed a leakage current of less than 10−12A.