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An in situ source-template-interface reaction route is used for nanocasting synthesis of 3D N-doped hierarchical carbon monolith (NHPCM) composed of interconnected, branched mesoporous rods because hierarchical porous silicon oxynitride monolith plays two roles of inorganic solid N source and template. The outstanding structural properties of NHPCM render it an excellent metal-free electrocatalyst for oxygen reduction.