Seeking　an　efficient　and　stable　cocatalyst　is　of　importance　for　semiconductor-based　photocatalytic　water　splitting　to　produce　hydrogen.　In　this　sense,　Mo-activation　of　VC　for　better　cocatalytic　properties　was　proposed　for　the　first　time,　aiming　to　attain　improved　hydrogen　generation　of　CdS.　Our　novel,　yet　facile　physical　preparation　method　permits　intimate　coupling　of　Mo-activated　VC　cocatalyst　to　CdS　(through　electrostatic　attraction　force),　thereby　promises　drastic　activity　enhancement　for　hydrogen　generation.　Results　indicate　the　best　VC-activating　competency　of　Mo　against　other　transition　metals　(Co,　Fe,　Ni,　Zn　and　Cu),　which　induces　highest　H2　productivity　of　CdS　after　modifying　with　Mo-activated　VC.　Under　optimum　setting,　CdS/Mo(0.38)-VC(5　wt%)　manifested　highest　photocatalytic　hydrogen　production　rate　of　2267　μmol　h−1　g−1,　associated　to　300　%　and　440　%　improvement　as　compared　to　that　of　CdS/VC(5　wt%)　and　pure　CdS,　respectively.　Such　activity　also　outperformed　those　that　yielded　by　MoSx-　or　noble　metals(Pt,　Au　or　Ag)-co-catalyzed　CdS,　attributed　to　the　promoted　interfacial　charges　transfer　and　lowered　overpotential　of　CdS/Mo(0.38)-VC(5　wt%)　in　hydrogen　generation.　Correspondingly,　high　apparent　hydrogen　production　quantum　efficiency　of　4.3　%　was　also　recorded　by　the　same　photocatalyst　at　420　nm.　In　term　of　stability　test,　CdS/Mo(0.38)-VC(5　wt%)　manifested　excellent　longevity　in　24　h　continuous　photoreaction　and　fair　recyclability　over　five　consecutive　photoreaction　cycles.　This　work　provides　a　new　insight　to　cocatalysts　design　and　synthesis,　thereby　realizing　economic　alternatives　to　precious　metal　(Pt,　Au,　Ag)　in　solar-derived　H2　production.　©　2022　Elsevier　B.V.