Abstract: A new monomer 5,8bis(furanyl)acenaphthenequinoxaline was synthesized by Stille cross coupling reaction and brominated. Its alternating coplymers of poly(2,5dioctyloxy1,4diethynylphenylenealt5,8bisfuranyl acenaphthenequinox) (PⅠ) and poly(2,5didodecyloxy1,4diethynylphenylenealt5,8bisfuranyl acenaphthenequinox) (PⅡ) were prepared with 2,5dialkoxy1,4diethynylbenzene. Both monomers and copolymers were characterized by FTIR, 1HNMR. UVVis、PL spectra and cyclic voltammetry were used to investigate their optical and electrochemical properties. Results show that monomer and copolymers of PⅠ and PⅡ maximum absorbancs of longer wavelength appear at 435、418、423 nm, corresponding emission peaks at 551、589、579 nm, respectively. The copolymers have maximum oxidation peaks of 1.54 V at the same potential, and exhibit irreversible electrochemical activities.