We utilized the metathesis reaction to synthesize a new type of multifunctional polymer that contains a conjugated backbone and a second-order NLO chromophore as a pendant group. The 1,6-heptadiyne derivatives bearing NLO chromophores were easily polymerized by using a metathesis catalyst to give corresponding polymers with large optical nonlinearities. Molecular structural characterizations for the resulting polymers were achieved by H-1- and C-13-NMR, FTIR, and UV-visible spectroscopies. Soluble polymers were obtained up to 72 mol % of chromophore monomer portion in the copolymer. These amorphous polymers exhibited good film-forming abilities and thermal stability. The electro-optic coefficient, r(33), of the poled polymer films was in the range of 0.5-10.1 pm/V, and the nonresonant values of the third-order NLO coefficient, chi((3)) was found to be about 10(-11) esu.