Novel crosslinkable polymers for second-order nonlinear optics (NLO) were synthesized using palladium catalyzed carbon-carbon coupling reaction. Nonconjugated α,ω-diyne derivatives (DANS-6, MONS-6) containing a choromophores were used as a crosslinkable moiety in polymer backbone. In order to improve the molecular weight and electro-optical properties of NLO active polymers, copolyme s were synthesized with diiodobenzene (DIB) and DANS-6 or MONS-6 with various feed ratio of diethyldipropargylmalonate (DEDPM). Polymerization yield was quantitative and the resulting polymers were completely soluble in organic solvents and easily spin cast onto the ITO substrate. During the present polymers were annealed at 160°C for 1 hr, the absorption intensity was drastically decreased which was due to the thermal crosslinking of the acetylenic unit in the polymer backbone.