The results of the study of charged particle emission in the course of the rupture of polymer film samples in the high vacuum have been presented. Regularities of ion emission at the last stages of the stretching are associated with peculiarities of the main crack’s intergrowing. Calculations of ion-motion trajectories within the crack were carried out. It was established that the ions emitted from the crack tip on the sample surface were recorded experimentally while the crack growing. The emitting region size and the emission current level were estimated. Mechanisms of formation of low-molecular ions during polymer fracture were discussed.