Two novel polyacetylenes bearing nonlinear optical chromophoric group poly(3-(4-[4-(n-butyloxy)phenylazophenyl]carbonyl)oxy-1-propyne) (poly(1a)) and poly(3-(4-[4-(n-heptyloxy)phenylazophenyl]carbonyl)-oxy-1-propyne) (poly(1b)) were synthesized with [Rh(nbd)Cl]2-Et3N as catalysts. These polyacetylenes are soluble by using an alkyl spacer and an alkyloxyl group as a substituent. They were characterized by FTIR, NMR, GPC and UV-Vis and their optical limiting and nonlinear optical properties were investigated using 8 ns pulse at 532 nm wavenumber. The results show that these soluble functional polyacetylenes possess optical limiting properties and large nonlinear optical properties and poly(1b) possesses better optical limiting and nonlinear optical properties than poly(1a).