Engineering of nanomaterials with abundant interfaces is vital but remain challenges for the electrocatalysts of renewable energy conversion systems. Benefitting from the efficient synthetic approach, a high degree of controlled design can be attained for the first time in the synthesis of hierarchical catalysts P-NiMo4N5@Ni, in which different morphologies arrays on nickel foam (NF) were achieved via introducing polyoxometalates with the capability of controlling the nucleation and crystal growth. Especially, the optimized twist braid nitrides nanorod arrays electrode P-NiMo4N5@Ni-1 with high surface-to-volume ratio of energetic actives exhibited unprecedented activity as a bifunctional electrocatalyst for water splitting, approaching 50 and 100 mA cm(-2) at low cell voltages of 1.59 and 1.66 V, respectively, which is one of the best electrolytic water catalysts. The insights gained through this work may provide novel approach for designing other arrays derived from polyoxometalates with unique surfaces as versatile electrode and provide a design platform to prepare the invertible oxides catalysts from nitrides at high potential with enhanced catalytic performance.