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　CoMoO　4　/CN　(CMO/CN)　photocatalyst　was　rationally　constructed　through　loading　CoMoO　4　nanorods　on　carbon　nitride　(CN)　nanosheets　via　a　direct　one-pot　calcination　method.　The　CMO/CN　Sscheme　heterojunction　exhibited　enhanced　surface　area,　fine　CN　dispersion,　rich　oxygen　vacancies,　and　accelerated　charge　separation/transfer　efficiency,　which　were　conducive　to　improving　photocatalytic　H　2　evolution　performance.　Of　note,　the　optimal　3　%CMO/CN　sample　displayed　the　highest　H　2　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　H　2　O　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.　(c)　2024　Published　by　Elsevier　Ltd　on　behalf　of　The　editorial　office　of　Journal　of　Materials　Science　&　Technology.