Prussian blue analogues (PBAs) with inherent ordered structures and abundant metal ion sites are widely explored as precursors for various electrochemical applications, including oxygen evolution reaction (OER). Using a range of characterization techniques including Fourier-transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and energy dispersive spectroscopy (EDS), this work discloses the process of replacement of K+ by NH4 + in the interstitial spaces of the CoFe PBA by a hot aqueous urea solution, which influences the transformation of PBAs under further heat treatment and the OER performance of the derivatives. After heat treatment at 400 °C under Ar flow, high-resolution transmission electron microscopy (HRTEM) images reveal that CoFe alloy nanoparticles grew on the crystalline cubes of CoFe PBA with K+, while CoFe PBA cubes with NH4 + become amorphous. Besides, the derivative of CoFe PBA with NH4 + (Ar-U-CoFe PBA) performs better than the derivative of CoFe PBA with K+ (Ar-CoFe PBA) in OER, registering a lower overpotential of 305 mV at 10 mA cm−2, a smaller Tafel slope of 36.1 mV dec−1, and better stability over a testing course of 20 h in 1.0 M KOH. A single-cell alkaline electrolyzer, using Ar-U-CoFe PBA and Pt/C for the anodic and cathodic catalyst, respectively, requires an initial cell voltage of 1.66 V to achieve 100 mA cm−2 at 80 °C, with negligible degradation after 100 h.