A novel electroactive poly(aryl ether ketone), with fixed conjugated length of oligoaniline(phenyl-capped aniline tetramer) in the main chain, was successfully synthesized via oxidative coupling polymerization method. The structure of poly(aryl ether ketone) was systematically studied by Fourier-transform infrared( FTIR) spectra, 1H NMR, and X-ray powder diffraction(XRD). And its electrochemical behavior was studied by cyclic voltammetry(CV) measurement. It was found that the obtained poly(aryl ether ketone) bearing phenyl-capped aniline tetramer segments had a reversible electrochemical property in the cyclic voltammetry, which was the same as that of polyaniline. Moreover, the thermal properties of poly(aryl ether ketone) were evaluated by thermogravimetric analysis(TGA).