Artificial photosynthesis offers a sustainable avenue to convert solar energy into fuels. An artificial photosynthetic system for hydrogen production comprises two essential components: a photosensitizer and a catalyst. Developing these components using earth-abundant elements is crucial for achieving sustainability. In this context, phosphinopyridyl ligands are used to synthesize a class of Ni(II) bis(chelate) complexes, which have been comprehensively characterized in both solid and solution phases. Significantly, these complexes serve as robust catalysts for homogeneous photocatalytic H2 evolution. In a system utilizing an organic photosensitizer and a sacrificial electron donor, an optimal turnover number of 27,100 is achieved in an alcohol−containing aqueous solution. A series of photophysical measurements and Density function theory calculations were conducted to elucidate the catalytic pathway. The sustained photocatalytic activity of these complexes stems from their distinct ligand system, which includes phosphine and pyridine donors that aid in stabilizing the low oxidation states of the Ni center.