The　search　for　a　low-cost　metal-free　cathode　material　with　excellent　mass　transfer　structure　and　catalytic　activity　in　oxygen　reduction　reaction　(ORR)　is　one　of　the　most　challenging　issues　in　fuel　cells.　In　this　work,　nitrogen-rich　m-phenylenediamine　is　introduced　into　the　synthesis　of　porous　carbon　spheres　to　tune　the　pore　structure　and　nitrogen-doped　active　sites.　As　a　result,　more　pyridinic　N　and　pyrrolic　N　functional　species　were　observed　at　the　interior　and　surface　of　the　carbon　spheres.　The　introduction　of　m-phenylenediamine　also　regulated　the　nucleating　of　precursors,　an　urchin-like　mesoporous　surface　structure　ensures　point　contact　and　less　agglomeration　between　each　particle　was　obtained.　With　optimized　proportion　of　micropores/mesopores　and　improved　nitrogen-contained　functional　species,　the　ORR　activity　can　be　remarkably　improved.　The　half-wave　potential　of　this　catalyst　could　achieve　to　0.81　V　(versus　RHE)　which　is　only　42　mV　lower　than　commercial　Pt/C　catalyst.　Furthermore,　the　optimized　cathode　catalyst　achieved　a　69　mW　cm(-2)　maximum　power　density　when　operated　in　direct　methanol　fuel　cells　at　room　temperature.