An ionic conjugated polyelectrolyte with bulky tetraphenylborate counter anions was easily synthesized via the ion-exchange reaction of poly(2-ethynyl-N-perfluorohexylpyridinium iodide) using sodium tetraphenylborate. The various instrumental methods revealed that the resulting polymer has a polyacetylene backbone system with bulky N-perfluorohexylpyridinium tetraphenylborate substituents The electro-optical properties and the electrochemical properties of the corresponding poly(2-ethynyl-N-perfluorohexylpyridinium tetraphenylborate) have been measured and discussed. The absorption spectrum of the polymer has absorption maximum peaks of 330 nm and 466 nm. The oxidation and reduction stability of the polymer was shown under the consecutive scans of 50 cycles. The material showed a diffusion process in the kinetics behavior, and the irreversible electrochemical behaviors were observed between the doping peaks and the undoping peaks.