Starting from hexabenzylhexaazaisowurtzitane(HBIW), five N-substituted hexaazaisowurtzitanes were synthesized via selective and catalytic hydrogenolysis debenzylation by using palladium compound as catalyst and under mild reaction conditions. In the debenzylation process, partial or all benzyl groups were displaced by other functional groups, such as H—, C₂H₅—, CHO— and CH₃CO—， etc. The structures of the resulting compounds were identified. The crystal structures of TADFIW and HAIW were characterized by X-ray diffraction. The crystal structure data and the crystal cell parameters are given. The five N-substituted hexaazaisowurtzitanes can be used as precursors for synthesis of hexanitrohexaazaisowurtzitane.