Hydrogen will be an important energy vector of the future, and improved efficiency in electrohydrolysis will accelerate this transition. In a fundamental study, we have prepared Co­(II) and Ni­(II) complexes of a new PNN type ligand N-((diphenylphosphanyl)­methyl)-2-amino-1,10-phenanthroline (dppmaphen) incorporating the photoactive 1,10-phenanthroline group and the strongly coordinating diphenylphosphine to obtain photoelectrochemical (PEC) catalysts [Co­(dppmaphen)2(NO3)2] (1) and [Ni­(dppmaphen)2Cl]Cl (2) which catalyzed the hydrogen evolution reaction (HER) in alkaline media (1 M KOH). Overpotentials (η10) of 430 (1) and 364 mV (2) could be reduced to 345 (1) and 284 mV (2) under Xe light irradiation. This irradiation generated photocurrent responses of 528 (1) and 357 uA/cm2 (2). Density function theory (DFT) calculation on the frontier orbitals of 1 and 2 were useful in understanding these differences in catalytic performance.