A new class of multifunctional polymers based on poly(l,6heptadiyne) derivatives with various functional groups such as carbazole unit for photoconductive polymers and nonlinear optical (NLO) chromophores for NLO polymers were synthesized by metathesis polymerization. The polymerizations were carried out with MoCI,-and WCI,-based catalysts. The catalytic activity of MoCI, was found to be greater than that of WCI , . The resulting polymers exhibited photoconductivity and large optical nonlinearity. These conjugated polymers have good solubility in common organic solvents, long-term stability toward air oxidation, and high electrical conductivity.