The chemical adsorption and active sites play a key role in electrocatalysis, so Ni-MOF/nickel foam was fabricated for efficiently reducing 4-nitrophenol (4-NP) without any sacrificial agents. The coordinated water molecules induced the formation of hydrogen bonds (H-bonds) with the nitro group, contributing to the self-enrichment of 4-NP. The reaction rate reached 0.351 μmol min-1 mg-1. Therefore, this work provides a new insight into the H-bond effect in the field of electrocatalysis.