Three-dimensional multi-doped porous carbon/graphene (Fe-Mt-SS-C) was prepared by carbonization of sewage sludge with template-assisted Fe-pillared montmorillonite. The material consisted of nanosheet- and particle- carbon had a high specific surface area (784.46 m2·g-1) and hierarchical porous structure of micro-, meso- and macropores. The prepared Fe-Mt-SS-C had a high degree of graphitization and large amount of defect atoms. The pyrolysis process made full use of the C, N, Fe, and S by turning them into the carbon framework of the as-obtained material in situ. Template-assisted Fe-pillared montmorillonite contributed to more characteristics of morphology and composition on Fe-Mt-SS-C than other three materials (SS-C, Mt-SS-C and Fe-SS-C), and enhanced the electrocatalytic ORR activity by providing more adsorption sites and the electronic structure, resulting in the increase of conductivity and electrochemical activity. The ORR activity performance of Fe-Mt-SS-C, including the value of onset potential (0.03 V) and E1/2 (-0.09 V), was better than that of commercial 20 wt% Pt/C (-0.02 V and -0.18 V, respectively). Moreover, the Fe-Mt-SS-C possessed excellent durability and outstanding immunity toward methanol crossover effects. Therefore, the resultant Fe-Mt-SS-C has great potential to applied as a high-efficiency ORR electrocatalyst, more importantly, it realizes the utilization of the sludge at the same time.