Hydrogen production via light-driven water splitting is a key process in the context of solar energy conversion. In this respect, the choice of suitable light-harvesting units appears as a major challenge, particularly as far as stability issues are concerned. In this work, we report on the use of CdTe/CdS QDs as photosensitizers for light-assisted hydrogen evolution in combination with a nickel bis(diphosphine) catalyst (1) and ascorbate as the sacrificial electron donor. QDs of different sizes (1.7–3.4 nm) and with different capping agents (MPA, MAA, and MSA) have been prepared and their performance assessed in the above-mentioned photocatalytic reaction. Detailed photophysical studies have been also accomplished to highlight the charge transfer processes relevant to the photocatalytic reaction. Hydrogen evolution is observed with remarkable efficiencies when compared to common coordination compounds like …