This study explores the behavior of the polypropylene/polybutylene succinate (PP*/PBS) polymer blend and its nanocomposites containing varying amounts of organically modified montmorillonite (OMMT) (Cloisite20: C20) (1%, 2%, 3%, 5%, and 10%) when subjected to electron beam irradiation in a scanning electron microscope (SEM). More specifically, we have studied the electrical properties of nanocomposites, in particular the trapping and transport of electrons in the material, as well as the emission of electrons. To examine the storage and spreading of injected electrical charge in nanocomposites under electron irradiation, we used time‐resolved current analysis method by measuring the induced currents (displacement and leakage currents). In order to verify whether there is a link between the electrical properties and the dispersion of the nanoclay particles in the polymer matrix, structural analyses were also carried out by x‐ray diffraction (XRD). The results revealed a significant increase in the equilibrium trapped charge as the amount of clay nanoparticles introduced into the matrix increased. This trend can be attributed to both an increase in the number of involved traps and the presence of interfaces that act as defect sites. This was checked by determining the energy distribution of the traps using Simmons' approach. Correlating the measured displacement and leakage currents allowed us to demonstrate that the presence of clay nanoparticles leads to a decrease in the electron emission efficiency.