Water splitting is considered one of the most promising approaches to power the globe without the risk of environmental pollution. The oxygen evolution reaction (OER) is even more challenging because the generation of only one oxygen molecule involves the transfer of four e^– and removal of four H⁺ ions from water. Thus, developing highly efficient catalysts to meet industrial requirements remains a focus of attention. Herein, the prominent role of Sn in accelerating the electron transfer kinetics of Ni₅P₄ nanosheets in OER is reported. The post catalytic survey elucidates that the electrochemically induced Ni–Sn oxides at the vicinity of phosphides are responsible for the observed catalytic activity, delivering current densities of 10, 30, and 100 mA cm^–2 at overpotentials of only 173 ± 5.2, 200 ±7.4, and 310 ± 5.5 mV, respectively. The density functional theory calculation also supports the experimental findings from the basis of the difference observed in density of states at the Fermi level in the presence/absence of Sn. This work underscores the role of Sn in OER and opens a promising avenue toward practical implementation of hydrogen production through water splitting and other catalytic reactions.