Poly[N-(6-azidohexyl)-2-ethynylpyridinium tetraphenylborate] (PAHEP-TPB) was prepared by the ion exchange reaction of the precursor polymer, poly[N(6-azidohexyl)-2-ethynylpyridinium iodide], by using sodium tetraphenylborate in methanol. The photoluminescence (PL) spectra of polymer showed that the photoluminescence peak is located at 599 nm, corresponding to a photon energy of 2.07 eV. The cyclic voltamograms of the polymer exhibited reversible electrochemical behaviors between the doped and undoped peaks. It was found that the kinetics of the redox process of PAHEP-TPB is controlled by the diffusion process mixed with the electron transfer process from the experiment of the oxidation current density of polymer versus the scan rate.