The article discusses a novel approach to enhance the efficiency of hydrogen evolution reaction (HER) in alkaline media using nickel hydroxide (Ni(OH)2) modified with trace iridium (Ir) atoms. By introducing Ir into the Ni(OH)2 matrix, the basal planes are activated for HER catalysis. Despite Ir dissolution during HER, electrooxidation stabilizes the catalytic activity, leading to the development of NiIr(OH)2-EO with exceptional performance. This modified catalyst exhibits high activity, robust stability, and superior mass-specific activity compared to existing electrocatalysts. The study also explores the use of NiIr(OH)2-EO in overall water splitting and urea-assisted electrolysis for energy-efficient hydrogen production. The work sheds light on utilizing transition metal hydroxides for efficient HER in alkaline media and provides insights into the mechanistic aspects of HER. Theoretical calculations and experimental measurements support the superior performance of NiIr(OH)2-EO in catalyzing HER and overall water splitting, making it a promising candidate for sustainable hydrogen production.