Photodriven charge-transfer dynamics and catalytic properties have been investigated for a hybrid system containing CdSe/ZnS core/shell quantum dots (QDs) and surface-bound molecular cobaloxime catalysts. The electron transfer from light-excited QDs to cobaloxime, revealed by optical transient absorption spectroscopy, takes place with an average time constant of 105 ps, followed a much slower charge recombination process with a time constant of >> 3 ns. More interestingly, we also observed photocatalytic hydrogen generation by this QD/cobaloxime hybrid system, with >10 000 turnovers of H-2 per QD in 10 h, using triethanolamine as a sacrificial electron donor. These results suggest that QD/cobaloxime hybrids succeed in coupling single-photon events with multielectron redox catalytic reactions, and such systems could have potential applications in long-lived artificial photosynthetic devices for fuel generation from sunlight.