Earth-abundant, environmentally friendly, and low-cost manganese oxide materials are promising resources for water oxidation catalysts in clean solar fuel applications. We here introduce a convenient and economic method for manufacturing stable and highly efficient manganese-oxide-based anodes for electrochemical water oxidation under neutral conditions. The electrodes were fabricated through thermal decomposition of acidic KMnO4 solution. The phase transitions of the manganese oxide film during calcination and thermal decomposition of KMnO4 were monitored with in situ heating transmission electron microscopy (TEM), in situ heating scanning transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy (STEM/EDX), and in situ heating powder X-ray diffraction (PXRD). In-depth monitoring of formation pathways and phase transformations by in situ techniques under high temperatures shed light upon the fabrication of efficient manganese oxides for energy conversion applications. After parameter optimizations, the best-performing manganese oxide catalyst was applied for water electrolysis for 100 h with a stable current density of 1.0 mA/cm2 at an overpotential of 490 mV in neutral pH. Post operando characterizations of key oxide film properties showed no significant changes. The readily commercially available precursor enables a simple and rapid fabrication method, and the promising stability and high performance of the herein developed electrodes render them quite promising for technological water splitting systems.