Thermal degradation of poly(ethylene oxide) (PEO) was studied under vacuum conditions. PEO macromolecules degrade predominantly by random chain scission of a backbone with elimination of oligomer fragments. The reactions include the mechanism of radical termination by disproportionation. The eliminated fragments form thin film deposits which have chemical composition close to the original PEO. Activation of the evaporated flux with a glow discharge leads to further fragmentation and recombination of the released species and can be used to tune the properties of the resulting thin films.