Zirconium ethoxide was synthesized by direct electrochemical reaction of anhydrous ethanol with sacrificial zirconium anode in the presence of tetraethylammonium chlorides (Et4NCl) as a conductive agent. The samples of products were characterized by Fourier transform infrared spectra (FT-IR) and Proton nuclear magnetic resonance spectroscopy (1H-NMR). The experiment results show that direct electrochemical synthesis of zirconium ethoxide has high current efficiency and abundant synthetic product compared with the conventional chemical methods. The behaviors of Zr in Et4NCl ethanol solutions were measured through potentiodynamic polarization, cyclic voltammetry, and potentiostatic current-time transient techniques. Effects of the temperature, scanning rate and the Et4NCl concentration were investigated. The results indicate that the electrochemical dissolution of the metal in anhydrous ethanol is a process of corrosive pitting. The rate of pit nucleation and pit growth increases with increasing of temperature and the Et4NCl concentration.