We report a discovery of the multiple coupled charge layer phenomenon in an insulating solid, SiO2, when irradiated by an electron beam with the aid of a Monte Carlo method. In tracing the transporting electrons, their encountered elastic, inelastic, and phonon scatterings, in conjunction with the influence of the electric field, are incorporated to model their transport more accurately. In handling charging, we consider the trapping of holes and energy-exhausted electrons on their drift paths, with the use of the electric-field-dependent drift velocity and trapping cross section. The emission of secondary electrons is modified by considering their trapping on the emission paths. Besides, the trapped charges may become detrapped under the electric field, which is also taken into account. Totally, six (three coupled) alternating charge layers are formed, with each layer having a thickness of about 0.1 μm, being parallel to the sample surface and existing merely along the beam incidence axis. The first layer is positive and is formed by secondary electron emission, while the sixth layer is negative and is formed by the extensive trapping of primary electrons. The middle four layers are formed by charge drift, in which electrons and holes move to opposite directions. However, the layer number remains unchanged with the increasing primary energy, since the charging involved in the simulation is negative, in which the primary electrons of different energies would be decelerated to a similar landing energy of 2–3 keV.