A new ionic conjugated polyacetylene with 3rd generation dendritic benzyl moieties was easily prepared by the activated polymerization of 2-ethynylpyridine by using 3rd generation dendritic benzyl bromide. The chemical structure of polymer was characterized by various instrumental methods to have the ionic conjugated polymer system bearing 3rd generation dendritic benzyl moieties. The photoluminescence spectra of polymer showed that the photoluminescence peak is located at 516 nm, corresponding to a photon energy of 2.41 eV. The cyclovoltamograms of this polymer exhibited reversible electrochemical behaviors between the doping and undoping peaks. The kinetics of the redox process of this polymer was found that it is almost controlled by the diffusion process from the experiment of the oxidation current density of polymer versus the scan rate.