Developing　highly　efficient　S-scheme　photocatalysts　is　a　subject　of　immense　interest　for　harnessing　solar　energy　towards　sustainable　hydrogen　production.　Herein,　a　novel　S-scheme　heterojunction　of　oxygen　vacancy-rich　CoMoO4/CN　(CMO/CN)　photocatalyst　was　rationally　constructed　through　loading　CoMoO4　nanorods　on　carbon　nitride　(CN)　nanosheets　via　a　direct　one-pot　calcination　method.　The　CMO/CN　S-scheme　heterojunction　exhibited　enhanced　surface　area,　fine　CN　dispersion,　rich　oxygen　vacancies,　and　accelerated　charge　separation/transfer　efficiency,　which　were　conducive　to　improving　photocatalytic　H2　evolution　performance.　Of　note,　the　optimal　3　%CMO/CN　sample　displayed　the　highest　H2　production　rate　of　8.35　mmol　g−1　h−1,　which　is　4.6　folds　that　of　pristine　CN.　In　situ　irradiated　X-ray　photoelectron　spectroscopy　(XPS)　and　electron　paramagnetic　resonance　(EPR)　characterizations　confirmed　the　S-scheme　charge　transfer　path　between　CN　and　CMO,　which　greatly　promoted　spatial　charge　separation.　Density　functional　theory　(DFT)　calculations　together　with　contact　angle　tests　revealed　the　reduced　activation　energies　for　H2O　dissociation　and　enhanced　hydrophilicity　of　the　CMO/CN.　The　CMO/CN　photocatalysts　also　presented　high　stability　and　fine　reusability.　This　work　may　provide　insights　into　the　combination　of　defect　engineering　and　heterojunction　designing　for　high-efficiency　solar-to-chemical　energy　conversion.　©　2024