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Transition metal phosphide (TMP) based electrocatalysts possessing special crystal and electronic structures attract broad attention in the field of electrocatalysis. Immense effort is made to optimize TMP catalysts aiming to satisfy the electrochemical catalysis performance. In this work, an environmentally friendly in situ green phosphating strategy and spatial limiting effect of the RuCo precursor is employed to fabricate the ruthenium nanoclusters anchored on cobalt phosphide hollow microspheres (Ru NCs/Co2P HMs). The obtained Ru NCs/Co2P HMs electrocatalysts exhibit high hydrogen evolution reaction (HER) activity at wide pH ranges, which require an overpotential of 77 mV to achieve the current density of 10 mA/cm2 in 0.5 mol/L H2SO4 and 118 mV in 1.0 mol/L KOH. Besides, the multifunctional Ru NCs/Co2P HMs exhibit good oxygen evolution reaction (OER) activity with an overpotential of 197 mV to reach the current density of 10 mA/cm2 in 0.5 mol/L H2SO4, which is below that of the commercial RuO2 electrocatalyst (248 mV). A two-electrode electrolyzer is assembled as well, in acid electrolyte, it achieves a current density of 10 mA/cm2 at a voltage of 1.53 V, which is superior to that of the benchmark of precious metal-based electrolyzer (1.58 V).