Dihydrogen (H2) production from sunlight should become one of the most important energy production means in the future. To reach this goal, low-cost and efficient photocatalysts still need to be discovered. Here we show that red near-IR luminescent metal cluster anions, once combined with pyrene-containing cations, are able to photocatalytically produce molecular hydrogen from water. The pyrene moieties act simultaneously as energy transmitters and as supramolecular linkers between the cluster anions and graphene. This association results in a hybrid material combining the emission abilities of pyrene and cluster moieties with the electronic conduction efficiency of graphene. Hydrogen evolution reaction (HER) studies show that this association induces a significant increase of H2 production compared to that produced separately by clusters or graphene. Considering the versatility of the strategy described to design this photocatalytic hybrid material, transition-metal clusters are promising candidates to develop new, environmentally friendly, and low-cost photocatalysts for HER.