The tetrahedral copper(I) diimine complex [Cu(pq)2]BF4 displays high photocatalytic activity for the H2 evolution reaction with a turnover number of 3564, thus representing the first type of a Cu(I) quinoxaline complex capable of catalyzing proton reduction. Electrochemical experiments indicate that molecular mechanisms prevail and DFT calculations provide in-depth insight into the catalytic pathway, suggesting that the coordinating nitrogens play crucial roles in proton exchange and hydrogen formation.