Heterogeneous or homogeneous polyelectrolyte influences on the solvolyses of t‐butyl chloride and α‐phenethyl chloride were studied. Anionic polymers enhanced the reaction rate by stabilizing the intermediate point dipole (ionic strength effect); cationic polymers with chloride ions as gegenions retarded the reaction by the mass action law (common ion salt effect), thus supporting the theory of Ingold et al. On the other hand, neutral polymer resins retarded the reaction probably because of the binding of the substrate on the resin surface. By the addition of a neutral polymer resin. Amberlite XAD‐4 the net steric course of the solvolysis of α‐phenethyl chloride was slightly changed from inversion to racernization, whereas anionic resins (Amberlite IR‐124) showed no effect. The heterogeneous polymer resin effect on the dearnination of α‐phenethyl amine was also studied. An anionic resin (IR‐124) retarded the reaction slightly and a neutrai resin (XAD‐4) retarded it to a great extent. A cationic resin (Dowex 1 × 8) accelerated the reaction, although slightly. The net steric course of the deamination was changed from inversion to racemization in the order XAD‐4 > Dowex 1 × 8 > IR 124. The heterogeneous polymer effect of the stereochemistry depended mainly on the hydrophobicity: i.e., the ability to bind the substrate on the surface of resin.