Hydride (H-) conduction is a new frontier related to hydrogen transport in solids. Here, a new H(-)conductive oxyhydride Ba2ScHO3 was successfully synthesized using a high-pressure technique. Powder X-ray and neutron diffraction experiments investigated the fact that Ba2ScHO3 adopts a K2NiF4-type structure with H- ions preferentially occupying the apical sites, as supported by theoretical calculations. Electrochemical impedance spectra showed that Ba2ScHO3 exhibited H- conduction and a conductivity of 5.2 x 10(-6) S cm(-1) at 300 degrees C. This value is much higher than that of BaScO2H, which has an ideal perovskite structure, suggesting the advantage of layered structures for H- conduction. Tuning site selectivity of H- ions in layered oxyhydrides might be a promising strategy for designing fast H- conductors applicable for novel electrochemical devices.