The development of efficient and cost-effective electrocatalysts for hydrogen evolution reaction (HER) is an urgent requirement but formidable challenge. In this work, Co and Mn were introduced into self-supported nickel-vanadium layered double hydroxide (NiV–LDH) to modulate electronic structure. The introduced Co and Mn can induce electron transfer among various cations to modulate the electronic structure, exerting a positive influence on the catalytic activity of HER. As a results, the samples with Co (NiVCo–LDH) and Mn (NiVMn–LDH) exhibits excellent HER activity. To achieve a current density of 10 mA cm–2 in 1.0 M KOH, NiVCo–LDH and NiVMn–LDH requiring overpotential of 135 mV and 123 mV, respectively. In contrast, NiV–LDH needed an overpotential of 198 mV to reach the same current density. The ideal performance of NiVCo–LDH and NiVMn–LDH offer a potential application in non-noble metal-based industrial electrolytic water splitting to produce high-purity hydrogen. Display omitted