Electron beam evaporated manganese oxide films display excellent electrochemical properties on post deposition oxidative annealing in air. The films annealed below 573 K are amorphous, exhibit minor deficiency in oxygen and are characterized by a specific discharge capacitance of 398 F g−1 at a discharge current of 1.1 A g−1 and 236 F g−1 at a discharge current of 5.5 A g−1. In terms of stability, these films retain 99.6% of their specific capacitance even after 400 cycles. The electrochemical properties of these films are explained in terms of their structure and composition which have been measured by X-ray diffraction and proton elastic backscattering spectrometry. In addition, the electrochemical properties are influenced by their morphology; the oxidatively annealed films contain nanometric, spherical and elongated grains which acquire extensive networking during electrochemical measurements.