MIS devices are fabricated by using a native oxide double‐layer insulator film. Capacitance and conductance measurements are carried out at different frequencies and temperatures to investigate the electrical characteristics of the native oxide double‐layer insulator film. The interface properties of the new double‐layer insulator are excellent as compared to the single‐layer MIS diodes. A marked reduction of interface state density as well as the anomalous frequency dependence of the MIS capacitance are observed. The surface composition and stoichiometry of oxides grown on InP by using the InP or alumina cathode are examined by using XPS technique. The XPS results show that the oxide layers are depleted of phosphorus and appeared to be indium‐rich oxides.