A series of chromophore-functionalized polyimide prepolymers with excellent processibility were prepared by a Michael addition reaction of diamine chromophore 2 with structurally different bismaleimide (BMI) monomers. The effects of the BMI moiety's structure and thermal curing condition on glass transition temperature (T-g) and thermal stability of the polyimides were studied by DSC, TCA, and FTIR. Among the five cured polyimides, PI3, bearing a sulfone moiety, exhibited the highest T-g and thermal decomposition temperature (T-d). Its corresponding prepolymer, PP3, was selected to evaluate NLO properties in a simultaneously poling and thermal polymerization process. A relatively large poling-order parameter was observed. The second-order nonlincar coefficient, d(33), was 25 pmN at 1061 nm fundamental wavelength. The second harmonic generation signal was almost without decay up to 170 degrees C.