Wide spread adaptation of green hydrogen can help to mitigate the serious climate issues, increasing global energy demands and the development of advanced electrocatalysts robust under industrial conditions is one of the key technological challenges. Herein, chromium‐doped nickel‐boride‐phosphide (Cr/NiBP) micro sphere (MS) electrocatalyst is demonstrated via a two‐step hydrothermal approach along with post‐annealing. The Cr/NiBP MS demonstrates low hydrogen evolution reaction and oxygen evaluation reaction over potentials of 78 and 250 mV at 100 mA cm⁻² in 1 m KOH, out performing most of the reported catalysts. The Cr/NiBP ǁ Cr/NiBP exhibits only 1.54 V at 100 mA cm⁻² in 1 m KOH and surpasses the benchmark of RuO₂ (+) ǁ Pt/C (−) up to 2000 mA cm⁻², which sets it as one of the best bifunctional electrocatalysts. Impressively, it maintains stable performance for over 240 h at 1000 mA cm⁻² in 6 m KOH at 60°C, demonstrating rapid response, anti‐corrosion resistance, and robust structural integrity to meet the industrial operational conditions. Further, Cr/NiBP ǁ Pt/C exhibits a super‐low cell‐voltage of 2.25 V at 2000 mA cm⁻². The small amount of Cr atoms incorporation can significantly enhance active sites and intrinsic properties, accelerating water dissociation and rapid intermediate formation.

Ultra-fine hydrogen produced by electrochemical water splitting without carbon emission is a high-density energy carrier, which could gradually substitute the usage of traditional fossil fuels. The development of high-performance electrocatalysts at affordable costs is one of the major research priorities in order to achieve the large-scale implementation of a green hydrogen supply chain. In this work, the development of a vanadium-doped FeBP (V-FeBP) microsphere croissant (MSC) electrocatalyst is demonstrated to exhibit efficient bi-functional water splitting for the first time. The FeBP MSC electrode is synthesized by a hydrothermal approach along with the systematic control of growth parameters such as precursor concentration, reaction duration, reaction temperature and post-annealing, etc. Then, the heteroatom doping of vanadium is performed on the best FeBP MSC by a simple soaking approach. The best optimized V-FeBP MSC demonstrates the low HER and OER overpotentials of 52 and 180 mV at 50 mA/cm² in 1 M KOH in a three-electrode system. In addition, the two-electrode system, i.e., V-FeBP || V-FeBP, demonstrates a comparable water-splitting performance to the benchmark electrodes of Pt/C || RuO₂ in 1 M KOH. Similarly, exceptional performance is also observed in natural sea water. The 3D MSC flower-like structure provides a very high surface area that favors rapid mass/electron-transport pathways, which improves the electrocatalytic activity. Further, the V-FeBP electrode is examined in different pH solutions and in terms of its stability under industrial operational conditions at 60 °C in 6 M KOH, and it shows excellent stability.