The compound of tetraacetyldibenzylhexaazaisowurtzitane (TADBIW) is the precursor of synthesizing the high energy density caged compound hexanitrohexaazaisowurtzitane (HNIW). TADBIW was obtained by hydrogenolysis of hexabenzylhexaazaisowurtzitane (HBIW). The hydrogenolysis product TADBIW contains a little amount of triacetyltribenzylhexaazaisowurzitane (TATBIW). It was proposed that the hydrogenolysis of HBIW would occur in a stepwise manner. Two compounds, diacetyltetrabenzylhexaazaisowurtzitance (DATBIW) and TATBIW, were synthesized by controlling the volumes of hydrogen that consumed during the hydrogenolysis debenzylation of HBIW. They are the intermediates of the hydrogenolysis of HBIW. The success of synthesizing these intermediates would be useful for researching the mechanism of the hydrogenolysis of HBIW. This is also useful for improving the hydrogenolysis process: increasing the amount of catalyst and prolonging the hours of reaction would produce high yields and enhance the purity of TADBIW.