This paper treats some theoretical premises determining peculiarities of acetylene polymerization and properties of polyene systems containing carboxy groups. Some kinetic mechanisms of the radiation polymerization of propiolic acid in the liquid phase were experimentally studied. It is shown that solid‐state polymerization of propiolic acid leads to the formation of the polymer with a higher molecular mass and greater effective conjugate length. The solid‐state polymerization of propiolic acid salts illustrates the dependence of the inclination to polymerization of ion metal radius. Some properties of polypropiolic acid and its salts were investigated, in particular, their inclination to photochemical reactions. A certain influence of the polyconjugate system and of the type of polyene chain configuration on the polypropiolic acid property as polyelectrolyte was discovered.