Wide using of polymer dielectrics in various branches of modem engineering stimulates the researches of changing these materials properties under the various conditions. Especially it concerned with materials subjected to various external effects. In submitted paper the results of research of charging condition formation in some polymer dielectrics and compound materials under the effect of strong electrical fields and various kinds of electrical discharges in air environment are presented. Correlation between the materials charging processes and their structure and technological preparing conditions are considered. New physical representations about the charging process mechanism in solid dielectric materials, subjected to effects of the strong electrical fields and discharges are extended. Formation the electrical charge of anomaly high density up to (10-7-10-8) C/cm2 in researched materials and revealing it charge only at heating a material is found out. Opportunities of control the process of charge injection in a material are analyzed.