Alkyne-containing polymers, obtained by the radical polymerization of 4-substituted conjugated enynes (CH2=CH-Cequivalent toC-R: R-= Ph- and n-Bu-), were subjected to polymer reactions through their alkyne moieties. That is, the radical addition of a thiol fragment, the hydrosilylation, and reduction via the hydroalumination were carried out to give polymers bearing alkenyl sulfide, alkenylsilane, and alkene moieties, respectively.