Metal hydrogen storage materials have been the focus of intensive research in the field of hydrogen-based economy. An outstanding question is that the number of hydrogen atoms accommodated in metal hydrides is generally much below the number of interstices, which limits their hydrogen storage capacities. Unlike traditional FCC metal hydrides where hydrogen can only occupy tetrahedral interstices, this study demonstrates that hydrogen can also occupy octahedral interstices in FCC high entropy alloy (HEA) hydrides, which leads to the violation of the Switendick criterion. For Ti25V25Nb25Ta25 and Ti25V25Nb25Zr25 HEAs, nearly 20% and 17.5% of octahedral interstices can be occupied by hydrogen, respectively. The anomalous hydrogen occupation mainly originates from the intrinsic electron delocalization between hydrogen atoms in HEA hydrides, which presents a sharp contrast to traditional metal hydrides. Such electron delocalization decreases repulsive interactions between hydrogens and promotes the electron localization at octahedral interstices. Additionally, this study reveals that hydrogen occupation at octahedral interstices enhances the structural disordering and decreases the thermal stability of HEA hydrides, which will be beneficial to reduce the dehydrogenation temperature. The presented results may provide a new strategy for the design of high-density storage materials.