We demonstrate a facile synthetic route to functional disubstituted polyacetylenes bearing highly polar groups based on polymer reactions. A pentafluorophenyl (PFP) ester-containing diphenylacetylene was designed and polymerized to obtain PFP activated ester-functionalized disubstituted polyacetylene (P1). P1 was used as a parent polymer to further react separately with diverse amines, giving rise to a series of functional disubstituted polyacetylenes with a chiral moiety and hydroxyl and carboxyl groups in high yields under mild condition. Spectral characterization data indicated that the polymers' structures were well consistent with the expected results. The helicity and emission property of polymers were also studied.