In this article we present the results of time-of-flight mass spectrometry of volatile products formed during the electrical breakdown of polyethylene terephthalate and polypropylene polymer films in high vacuum. During the breakdown of films, all the substance emitted from the breakdown channel is a gas of low-molecular products of destruction of macromolecules. The breakdown mass spectra do not contain lines of carbon molecules, the presence of which could indicate carbonation of the channel. To explain the formation of charge carriers, the ionization mechanism of destruction of macromolecules in an electric field is used without the involvement of impact ionization. The final stage of electrical breakdown (the flow of a high-density conduction current) occurs when the critical concentration of traps and electrons ~1024 m-3 is reached. Keywords: electrical breakdown, mass spectrometry, thermodestruction, ionization, macromolecule, trap.