Developing a cost-effective, efficient, and stable oxygen evolution reaction (OER) catalyst is of great importance for sustainable energy conversion and storage. In this study, we report a facile one-step fabrication of cationic surfactant-assisted Prussian blue analogues (PBAs) Mx[Fe(CN)5CH3C6H4NH2]∙yC19H34NBr abbreviated as SF[Fe-Tol-M] (where SF = N-tridecyl-3-methylpyridinium bromide and M = Mn, Co and Ni) as efficient heterogeneous OER electrocatalysts. The electrocatalysts have been characterized by Fourier transform infrared (FT-IR) spectroscopy, powder X-ray diffraction (PXRD), scanning electron microscopy (SEM) coupled with energy dispersive X-ray (EDX) analysis, and X-ray photoelectron spectroscopy (XPS). In the presence of cationic surfactant (SF), PBAs-based electrodes showed enhanced redox current, high surface area and robust stability compared to the recently reported PBAs. SF[Fe-Tol-Co] hybrid catalyst shows superior electrochemical OER activity with a much lower over-potential (610 mV) to attain the current density of 10 mA cm−2 with the Tafel slope value of 103 mV·dec−1 than that for SF[Fe-Tol-Ni] and SF[Fe-Tol-Mn]. Moreover, the electrochemical impedance spectroscopy (EIS) unveiled that SF[Fe-Tol-Co] exhibits smaller charge transfer resistance, which results in a faster kinetics towards OER. Furthermore, SF[Fe-Tol-Co] offered excellent stability for continues oxygen production over extended reaction time. This work provides a surface assisted facile electrode fabrication approach for developing binder-free OER electrocatalysts for efficient water oxidation.