Developing electrochemically active molecules is of great significance for expanding various electrochemical devices. Through the electrochemical workstation test, a small benzil molecule with good cyclic voltammetric reversibility within the electrochemical window of a mixed solution of ethanol and water was discovered. At the same time, based on simple benzoin condensation and oxidative dehydrogenation coupling reactions, a polybenzil polymer material (DB-YHH) was prepared. Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy and permeation gel chromatography test results prove that DB-YHH is a class of conjugated polymers containing ortho-biscarbonyl groups. The polybenzil is easy to be synthesized and the polymerization reaction is highly atom economic. The electrochemical workstation test results show that polybenzyl has a good electrochemical reversibility in 1 mol/L KOH aqueous electrolyte, with a reduction potential of 0.206 V vs RHE, an oxidation potential of 0.082 V vs RHE, and a reversible potential difference of 124 mV. This work opens up a new method for the preparation of polybenzil by benzoin condensation reaction followed by oxidative dehydrogenation, which may lead to the birth of a series of new polybenzil polymers. Moreover, the good electrochemical activity of polybenzil in water electrolyte may have potential applications in various types of electrochemical cell.