In order to improve the activity of hydrogenolytic debenzylation catalyst and reduce the dosage of noble metal palladium during the synthesis of hexanitrohexaazaisowurtzitane（CL-20）， carbon supports were prepared by ball-milling/carbonization method using sodium gluconate as a raw material. The effects of carbonization temperature， heating rate and additive addition of sodium gluconate on the support structure and the catalytic activity of the corresponding Pd（OH）₂/C catalysts in the hydrogenolytic debenzylation of hexabenzylhexaazaisowurtzitane（HBIW） and tetraacetyldibenzylhexaazaisowutzitane（TADB） were explored. The pore structure， particle morphology， crystal phase structure， chemical composition and surface chemical properties of carbon supports were characterized by nitrogen sorption isotherm measurement（BET）， scanning electron microscope（SEM）， transmission electron microscopy（TEM）， powder X-ray diffraction（XRD）， element analysis and temperature programmed desorption （TPD）. The results show that the optimized carbonization condition of sodium gluconate was calcination at 700 ℃ with a heating rate of 10 ℃·min^-1 in the presence of additive， NaHCO₃， which could adjust the puffing carbonization of sodium gluconate. The received carbon supports have rich hierarchical pore structure and appropriate amount of surface oxygen containing groups， and the corresponding Pd（OH）₂/C catalysts exhibit high activities in the hydrogenolytic debenzylation reaction of HBIW and TADB.