Spray deposited MnO2 thin films onto glass substrate were subjected to a post-deposition heat treatment and the effects of temperature on electrical transport properties were studied in details. The heating and cooling cycles of the samples are reversible after successive heat-treatments in air and vacuum. The films were polycrystalline in structure and the oxygen chemisorption–desorption process was found to play an important role in controlling the electronic properties. Various grain-boundary and energy band parameters were calculated by taking conventional extrinsic semiconductor theory and grain boundary trapping models into account. The samples were non-degenerate n-type semiconductors. The transport properties are interpreted in terms of Seto's model which was proposed for polycrystalline semiconducting films. The inter-crystallite boundaries of the thin films play an important role in the transport properties.