Five redox polymer precursors, poly(5-vinyl-1,3-benzodioxole) (poly I), poly(3,4-dimethoxystyrene) (poly II), poly(2,3-dimethoxystyrene) (poly III), poly(6-vinyl-1,4-benzodioxane) (poly IV) and poly(4-vinyl-1,3-benzodioxole) (poly V), underwent aminomethylation and sulfonation reactions. Phthalimidomethylation was realized via the Gabriel reaction, which upon hydrazinolysis yielded aminomethylated resins, valuable intermediates for subsequent modification. The sulfonation of these polymers with chlorosulfonic acid followed by treatment with tetramethylammonium chloride afforded new polyelectrolytes.