Efficient oxygen evolution reaction (OER) electrocatalyst is essential for water electrolysis. Herein, high -performance NiFe-based layered double hydroxides (LDH), phosphide and sulfide OER pre-catalysts were fabricated and their distinct activity was unveiled. The as-prepared NixFe1-xS exhibits ultralow OER overpotential of 122 mV at 10 mA cm(-2) in 1 M KOH. The alkali-electrolyzer using NixFe1-xS electrodes achieve superior performance exhibiting a voltage of 1.46 V at 10 mA cm(-2). Experimental analysis reveals that, during OER, Fe dissolution into electrolyte occurs for NiFe LDH and NixFe1-xP, which were both converted into NiOOH, well explaining their similar activity. Interestingly, Fe dissolution is significantly mitigated in NixFe1-xS, forming partially oxidized Fe2O3/FeOOH species. Theoretical calculations confirmed that Fe2O3/FeOOH is responsible for the enhanced OER energetics of NixFe1-xS. These observations provide new insights on the distinct activity of NiFe-based electrocatalysts, guiding their rational design as well.