Advances in non-noble-metal electrocatalysts for sustainable hydrogen evolution reactions (HERs) have had a significant impact on the production of renewable clean energy (H 2 ). Benefitting from high-efficiency synthesis methods, a controlled catalyst P-CoMoO 4 @Ni with a hierarchical structure with different morphologies on the surface of nickel foam (NF) has been synthesized. In particular, the optimized nanoflower oxide array electrode P-CoMoO 4 @Ni-1 performed as the best catalyst for HER with a large specific surface area and low charge-transfer resistance and was capable of delivering current densities of 100 and 150 mA cm −2 under low overpotentials of 98 and 162 mV, respectively. In addition, this work demonstrated that catalyst arrays adopted by polyoxometalates (POMs) as precursors with uniform nanoflower structures might be able to improve electrocatalytic performance as well as provide fundamental research of catalyst materials with high efficiency at low potentials in HER.