In addition, previous studies have shown the incorporation of a third transition metal into forming ternary PBAs (such as NiFeSe , NiCoFe , (Mn0.5Cu0.5)Fe , and CoFeSe , etc.) to be an effective way to boost catalytic activity of binary PBAs owing to the suitable regulation of electronic structure, which can optimize the value of (ΔGO*-ΔGHO*) and coordination environment of active centers. This lets us investigate quaternary PBAs that hold the potential to further facilitate the OER catalytic properties through more favorably tuned electronic structures. To achieve this, first-row (3d) transition-metal elements such as Cr, Mn, Fe, Co, Ni, Cu, Zn, etc. are the most common elements for synthesizing catalysts in OER, taken into consideration in this work. To address the aforementioned critical aspects, a cubic quaternary CoNiCuFe-PBA catalyst was synthesized via a low-cost and simple coprecipitation method at room temperature, and the corresponding amorphous CoNiCuFe-Oxide catalyst was fabricated by further pyrolysis at 500 °C in air. Surprisingly, well-crystallized CoNiCuFe-PBA was found to possess anomalous OER activity than the amorphized CoNiCuFe-Oxide. Specifically, a more abundant MOOH active species generated on the CoNiCuFe-PBA catalyst surface compared to its counterpart was identified by in situ Raman spectra. The high valance state of Co and Ni in the better crystalline cubic CoNiCuFe-PBA catalyst is suggested to promote surface hydroxylation, further favoring the origin of the stable and active phase for OER in long-term tests.