The radical and cation copolymerization of 1,4-benzoquinone and phenylacetylene in monomer mass and in medium of various solvents has been investigated. By physical-chemical methods the structure of the prepared cooligomers, (= 750–1550) has been established. It has been revealed that the synthesized polyconjugated polyfunctional cooligomers possess thermostability, semiconductor and paramagnetic properties. These cooligomers show high reactivity at reactions of electron-exchange and interaction with anhydrides of organic acids and epoxide compounds