The　emergence　of　Mo-based　hybrid　zeolitic　imidazolate　frameworks　(HZIFs)　with　MoO(4)units　brings　substantial　advantages　to　design　and　synthesize　complex　Mo-based　electrocatalyst　that　are　not　expected　in　their　conventional　synthesis　path.　Herein,　as　a　newly　proposed　concept,　a　facile　temperature-induced　on-site　conversion　approach　(TOCA)　is　developed　to　realize　the　transformation　of　MoO(4)units　to　C-Mo-S　triatomic　coordination　in　hierarchical　hollow　architecture.　The　optimized　hybrid　(denoted　as　MoCS(x)1000)　shows　accelerating　oxygen　reduction　reaction　(ORR)　kinetics　and　excellent　stability,　which　are　superior　to　the　most　reported　Mo-based　catalysts.　Extended　X-ray　adsorption　fine　structure　(EXAFS)　analysis　and　computational　studies　reveal　that　the　near-range　electronic　steering　at　C-Mo-S　triatomic-coordinated　nanointerface　guarantees　moderate　ORR　intermediates　adsorption　and　thus　is　responsible　for　the　boosted　ORR　activity.　This　work　sheds　light　on　exploring　the　intrinsic　activity　of　catalysts　by　interfacial　electronic　steering.