The　design　and　synthesis　of　non-precious　metal　dual-functional　electrocatalysts　through　the　modulation　of　electronic　structure　are　important　for　the　development　of　renewable　hydrogen　energy.　Herein,　MnS2/MnO2-CC　heterostructure　dual-functional　catalysts　with　ultrathin　nanosheets　were　prepared　by　a　two-step　electrodeposition　method　for　efficient　acidic　hydrogen　evolution　reaction　(HER)　and　degradation　of　organic　wastewater　(such　as　methylene　blue　(MB)).　The　electronic　structure　of　Mn　atoms　at　the　MnS2/MnO2-CC　heterostructure　interface　is　reconfigured　under　the　joint　action　of　S　and　O　atoms.　Theoretical　calculations　show　that　the　Mn　d-band　electron　distribution　in　MnS2/MnO2-CC　catalyst　has　higher　occupied　states　near　the　Fermi　level　compared　to　the　MnO2　and　MnS2　catalysts,　which　indicates　that　MnS2/MnO2-CC　catalyst　has　better　electron　transfer　capability　and　catalytic　activity.　The　MnS2/MnO2-CC　catalysts　require　overpotential　of　only　66　and　116　mV　to　reach　current　density　of　10　and　100　mA　cm−2　in　MB/H2SO4　media.　The　MnS2/MnO2-CC　catalyst　also　has　a　low　Tafel　slope　(26.72　mV　dec−1)　and　excellent　stability　(the　performance　does　not　decay　after　20　h　of　testing).　In　addition,　the　MB　removal　efficiency　of　the　MnS2/MnO2-CC　catalyst　with　a　better　kinetic　rate　(0.0226)　can　reach　97.76%,　which　is　much　higher　than　that　of　the　MnOx-CC　catalyst　(72.10%).　This　strategy　provides　a　new　way　to　develop　efficient　and　stable　non-precious　metal　dual-functional　electrocatalysts　for　HER　and　organic　wastewater　degradation.　©　2023