AbstractThe design and production of active, durable, and nonprecious electrocatalysts toward alkaline hydrogen oxidation and evolution reactions (HOR/HER) are extremely appealing for the implementation of hydrogen economy, but remain challenging. Here, we report a facile electric shock synthesis of an efficient, stable, and inexpensive NiCoCuMoW multi‐element alloy on Ni foam (NiCoCuMoW) as a bifunctional electrocatalyst for both HOR and HER. For the HOR, the current density of NiCoCuMoW could reach ∼11.2 mA cm–2when the overpotential is 100 mV, higher than that for commercial Pt/C (∼7.2 mA cm–2) and control alloy samples with less elements, along with superior CO tolerance. Moreover, for the HER, the overpotential at 10 mA cm−2for NiCoCuMoW is only 21 mV, along with a Tafel slope of low to 63.7 mV dec−1, rivaling the commercial Pt/C as well (35 mV and 109.7 mV dec−1). Density functional theory calculations indicate that alloying Ni, Co, Cu, Mo, and W can tune the electronic structure of individual metals and provide multiple active sites to optimize the hydrogen and hydroxyl intermediates adsorption, collaboratively resulting in enhanced electrocatalytic activity.