ABSTRACTProcessable polymeric nonlinear optical materials can be synthesized by functionalizing a glassy macromolecule with chromophores having large quadratic hyperpolarizabilities, followed by poling in an electric field. In the present case, the functionalization of polystyrene with 4- (4-nitrophenylaza)(N-ethyl)(2-hydroxyethyl))aniline, 4-(4-N,N-dimethylaminostyryl) pyridine, and N-(4-nitrophenyl)-L-prolinol is described. Particularly noteworthy is the high level of chromophore units that can be incorporated into transparent films of these materials, the high second harmonic coefficients that can be achieved (as high as d33 – 11 × 10-9 esu at 1064 nm), and the long-term temporal stability of the second harmonic generation capacity.