In the present study, graphite/alumina composites are fabricated via reductive sintering of gel-casted green bodies with structurally controlled cross-linked epoxy polymers for the first time. The cross-linking degrees of polymers are tuned by the amount ratio of epoxy monomer/polyvinyl alcohol cross-linker utilized in gel-casting process. Superior electrical properties with respect to 5-fold enhanced electrical conductivity and 2-fold higher carrier mobility are successfully achieved in graphite/alumina composite fabricated from cross-linked epoxy polymer, whose phenomenon is attributed to the excellent conductive path in ceramic matrix established by highly uniform network with improved graphitization degree.