Well-defined multifunctional polymers, bearing charge transporting (CT) and nonlinear optical (NLO) functionality covalently attached to each repeat unit, were synthesized and characterized. High glass transition temperature (T-g) polyurethanes, comprised of alternating CT and NLO units, were synthesized from NLO functionalized diols and N,N-bis(4-isocyanatophenyl)aniline. Polyimides, exhibiting high thermal stabilities, were obtained from a fluorinated dianhydride and a multifunctional (CT and NLO) diamine. The functionalized polyimides were obtained in two ways: by formation of a brominated polyimide derivative and subsequent Heck coupling with styrene derivatives; and direct polycondensation of a fully functionalized triarylamine diamine analog with 4,4＇-(hexafluoroisopropylidene)diphthalic anhydride (6-FDA). Phosphonate ester and nitro electron-withdrawing groups were utilized in the NLO moieties. (C) 2000