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We report on an all-solid-state battery that employs a closo-type complex hydride solid electrolyte and a LiCoO2 cathode.Interfacial modification between the solid electrolyte and cathode with a LiNbO3 buffer layer enables reversible charge-discharge cycling with a cell voltage of 3.9V (vs.Li+/Li) at room temperature.Electrochemical analyses clarify that the given modification effectively suppresses side reactions at the cathode/solid electrolyte interface.The interracial resistance is lowered by ca.10 times with a 5 nm thick LiNbO3 buffer layer compared to that without a buffer layer,so that a discharge capacity of 109 mAh g-1 is achieved.These results suggest that interracial modification can be a viable approach to the development of high-voltage all-solid-state batteries using closo-type complex hydride solid electrolytes and oxide cathodes.