After the preparation of hexahydro-1, 3, 5-trinitro-1, 3, 5-triazine/resorcinol-formaldehyde (RDX/RF) nanostructured composite energetic materials,the pore structures of RF aerogel and RDX/RF were characterized. Specific areas,total pore volumes and average pore diameters of RDX/RF with 10%,30%,50%,70%,80% RDX were calculated. Adsorption-desorption isotherm curves,middle pores distribution curves and micropores distribution curves were compared together. Compared with RF aerogel,the specific area,total pore volume,composite materials have small and large average pore diameter. The mean diameter pf nano-crystal RDX in RDX/RF is 34-38 nm. The changes were caused by the filling of detonator RDX. The changes in adsorption-desorption isotherm,middle pore and micropore distribution,and total middle pore volumes of RDX/RF indicate that detonator RDX plays a key role in influencing middle pore of RF aerogel.