Alkaline membrane fuel cell (AMFC) is an electrochemical conversion device, which produces electrical energy through oxygen reduction reaction. Platinum metal has been used as a catalyst since its inception, but expansiveness and low stability at alkaline medium are the major obstacles in its commercialization. Manganese dioxide (MnO₂) has been used for various energy and environmental applications; however the thermal sensitive MnO₂ has not been studies yet. Based on metal cost α-MnO₂ has higher specific activity as compared to commercial Pt/C catalyst, thus considered to be potential cathode material for AMFCs. Herein α-MnO₂ nanorods have been produced by treating MnO₂ under different temperature (300, 400 and 500 ⁰C) and their physical and electrochemical properties were explored. By providing optimum gas pressure the oxygen vacancies were induced thermally in the α-MnO₂ nanorods. Oxygen vacancies of α-MnO₂ nanorods were explored by high-angle angular dark field (HAADF). It was also found from X-ray photoelectron spectroscopy (XPS) analysis that oxygen vacancies were more strengthened with increasing temperature. The samples were investigated for oxygen reduction reaction (ORR), it was found that sample treated at 400 ⁰C has the excellent ORR performance, higher long term stability in alkaline medium and best methanol tolerance as compared to commercial Pt/C. these properties have been imparted to the catalyst due to preferential growth of catalyst at (211) plane and optimized oxygen vacancies creation. The α-MnO₂ nanorods became longer and thinner with increasing temperature and it was believed that this was another reason for better performance. This work implied that α-MnO₂ nanorods are temperature sensitive and best ORR performance can be achieved by optimizing calcination temperature.