In this paper, a detailed study of the electrochemical behavior of zirconium in the molten LiF-KF-ZrF4 system on an inert molybdenum electrode was carried out at 600 °C. Several electrochemical techniques were employed such as cyclic voltammetry, chronoamperometry and square wave voltammetry. The reduction of zirconium was found to be a multi-step process that at the potentials of 1.15, 1.50 and 1.62 V versus Pt, the corresponding cathodic reactions of Zr4+/Zr2+, Zr2+/Zr+ and Zr+/Zr occurred. The result was further confirmed by the theoretical calculation of the number of transferred electrons according to the cyclic voltammetry and square wave voltammetry analysis. Moreover, based on the cyclic voltammograms, the diffusion coefficient of Zr4+ ions in the eutectic LiF-KF containing 1 wt% ZrF4 at 600 °C was estimated to be about 8.31 × 10-6 cm2 s-1. The present electrochemical study on zirconium in the molten fluoride system will be a theoretical reference for future zirconium electrorefining from Zr alloy or scraps.