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We report on the experimental study of electrical instabilities in thin film structures on the basis of molybdenum oxides. Thin films of molybdenum oxide are obtained by thermal vacuum evaporation and anodic oxidation. The results of X-ray structural analysis, investigation of optical and electrical properties, are presented. It is shown that the initial vacuum-deposited oxide represents amorphous MoO 3 . In the MOM (metal-oxide-metal) structures with Mo oxide films obtained by the two methods, the effect of electrical switching with an S-shaped current-voltage characteristic is found. We put forward a hypothesis according to which the switching mechanism is associated with the development of electrical instability caused by the insulator-to-metal transition in Mo 8 O 23 . The switching channel, comprising this lower valence oxide, emerges in the initial film during the process of electrical forming of the MOM structure. The obtained results indicate the possibility of application of these structures in oxide micro-and nanoelectronics as electronic switches and other electronic devices.