Strategically engineering electrocatalysts with optimized interfacial electronic architectures and accelerated reaction dynamics is pivotal for augmenting hydrogen generation via alkaline water electrolysis on an industrial scale. Herein, a novel triple-interface heterostructure Ni 3 Se 4 -NiSe 2 -Co 3 O 4 nanoarrays are designed anchored on Ti 3 C 2 T x MXene (Ni 3 Se 4 -NiSe 2 -Co 3 O 4 /MXene) with significant work function difference (ΔΦ) as bifunctional electrocatalysts for water electrolysis. Theoretical calculations combined with experiments uncover the pivotal role of the interface-induced electric field in steering charge redistribution, which in turn modulates the adsorption and desorption kinetics of reaction intermediates. Furthermore, the synergistic interaction between Ni 3 Se 4 -NiSe 2 -Co 3 O 4 and Ti 3 C 2 T x MXene nanosheets endows the hybrids with a large electrochemical surface area, abundantly active sites, and high conductivity. Thus, Ni 3 Se 4 -NiSe 2 -Co 3 O 4 /MXene manifests exceptional catalytic prowess for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). In addition, the Ni 3 Se 4 -NiSe 2 -Co 3 O 4 /MXene electrocatalyst in the water electrolyzer delivers excellent performance and maintains commendable stability beyond 100 h of electrocatalytic operation.