A facile, cost and resource-effective method has been developed to prepare self-supported, highly efficient and long-term stable Pt-like CoxB-[0.2]P-O electrocatalyst for HER. A comprehensive scale-bridging investigation of the microstructure and chemistry of the complete electrode with emphasis on the active catalyst material has been employed to explain the enhanced electrocatalytic and Pt-competitive HER performance of the electrode in comparison to previous CoxB based catalysts.