Manganese oxide films for lithium secondary batteries were prepared using a reactive evaporation method. Mn was evaporated from a molybdenum boat by resistive heating and deposited on a glass slide under oxygen atmosphere. These films were examined with x-ray photoelectron spectroscopy (XPS) and x-ray diffraction. The Mn oxide films with a wide valency of Mn were prepared in this study. A rapid change of the back pressure was found as the deposition of Mn was started. This implies that Mn atoms start to react with O2. This means that in situ detection of reactive evaporation process can be utilized.