The influence of the electronegativity of phases, which is controlled by composite crystallization under the conditions of the effect of the electric discharge and covalence of piezophase cations, on the formation mechanism of the stable electret effect is determined. The specific features of the formation of the electret effect in composites based on polyolefins (HDPE, PP), fluorine-containing polymers (F42), and ferroelectric piezoelectric ceramics of the family of lead zirconate–titanate (Pb(Zr,Ti)O_3) crystallized under conditions of the effect of electric discharge plasma, are revealed. A physical model of electret composites taking into account the role of homocharges and heterocharges formed in a composite by its dispersion with piezoceramic particles of various structures—rhombohedral, tetragonal, and heterogeneous—is proposed.