Understanding　the　relationship　of　competitive　adsorption　between　reactants　is　the　prerequisite　for　high　activity　and　selectivity　in　heterogeneous　catalysis,　especially　the　difference　between　the　adsorption　energies　(Eads)　of　two　reactive　intermediates　in　Langmuir–Hinshelwood　(L−H)　models.　Using　oxidative　dehydrogenation　of　hydrogen　sulfide　(H2S-ODH)　as　a　probe,　we　develop　various　metal　single　atoms　on　nitrogen-doped　carbon　(M-NDC)　catalysts　for　controlling　Eads-H2S,　Eads-O2　and　investigating　the　difference　in　activity　and　selectivity.　Combining　theoretical　and　experimental　results,　a　Sabatier　relationship　between　the　catalytic　performance　and　Eads-O2/Eads-H2S　emerges.　Mn-NDC　as　the　optimal　catalyst　shows　excellent　H2S　conversion　(＞90　%)　and　sulfur　selectivity　(＞90　%)　in　a　wide　range　of　O2　concentrations　over　100　h.　Such　a　high-efficiency　performance　is　attributed　to　appropriate　Eads-H2S　and　Eads-O2　on　Mn-N4　sites,　boosting　redox　cycle　between　Mn2+　and　Mn3+,　as　well　as　preferential　formation　of　sulfur.　This　work　provides　a　fundamental　guidance　for　designing　Sabatier　optimal　catalysts　in　L−H　models.　©　2024　Wiley-VCH　GmbH.