Two novel high molecular weight functional polyacetylenes bearing oxadiazole groups as pendants, poly(2-(4-decyloxyphenyl)-5-(4-ethynylphenyl)-1, 3, 4-oxadiazole) (P1) and poly(2-(4-butyloxyphenyl)-5-(4-ethynylphenyl)-1, 3, 4-oxadiazole) (P2) were designed and synthesized by a multistep reaction route. The structures and properties were characterized and evaluated with FTIR, NMR, UV, TGA, GPC, optical-limiting (OL) and nonlinear optical (NLO) analyses. The incorporation of oxadiazole into polyacetylene significantly endows polyacetylenes with higher thermal stability and optical limiting property. The solubility, stereoregularity and optical properties of resultant polyacetylenes are obviously affected by flexible terminal alkoxy chain length. The cis olefinic structure content in polyacetylene backbone increases with increasing terminal alkoxy group length. The functional polyacetylene with the higher cis olefinic structure content shows higher thermal stability, better optical limiting property and larger third-order nonlinear optical performance. The optical limiting mechanism of resulting polymers was investigated, which is mainly originated from larger excitation state absorption cross-section of molecules to result in reverse saturable absorption.