A highly operative and inexpensive water oxidation scheme using an efficient nanoscale electrocatalyst is vastly demanded for optimum H₂ production, CO₂ reduction, and has attracted increased attention for chemical energy conversion. We present here a simple route to make efficient electrocatalytic colloidal nanoparticles of nickel out of mere metal ions in a simple borate buffer system. The simple and annealed Ni-colloidal nanoparticles (Ni-CNPs) resulted in a facile transformation into ultrafine films, which further activated the catalysts, while initiating OER just at the overpotential η = 250 mV (1.48 V vs. RHE) under benign conditions. They also showed high porosity and favorable kinetics while displaying impressive Tafel slopes of just 51 mV dec⁻¹, and a high TOF value of 0.79 s⁻¹ at 0.35 V was observed for Ni-CNPs/FTO₅₀₀. These electrocatalysts also showed long-term stability during the bulk water electrolysis experiment conducted for a continuous 20 hours without notable catalytic degradation, which ensures their economic benefits. The electrochemical data, CVs, kinetic study, short-term durability, extended catalytic stability, SEM analysis, and other supporting data provide compelling evidence that these non-precious, metal-based, electroactive, catalytic, colloidal thin-films (simple and annealed) with nanoscale morphological attributes presented promising catalytic performance under the conditions used herein.