A series of nickel complexes containing N₅-pentadentate ligands with different amine-to-pyridine ratios were studied for electrochemical H₂ production in neutral water and the one with a diamine–tripyridine ligand displays a TON of up to 308 000 over 60 h electrolysis at −1.25 V vs. SHE, with a Faradaic efficiency of ∼91%.