Kinetics of zirconium and aluminum electroreduction from the KF-AlF3-Al2O3-ZrO2 melts at a temperature of 750°C have been studied by means of voltammetry methods and stationary polarization. The effects of the ZrO2 additions, substrate material and polarizaE tion rate on the kinetics and the main features of the zirconium and aluminum electroreducE tion under stationary and nonstationary conditions were studied. It was shown that the zirE conium electroreduction is primary accompanied by diffusion difficulties and it is not reEversible. The limiting currents of the cathode process in the KF-AlF3-Al2O3-ZrO2 melts as well as diffusion coefficients of zirconiumEcontaining electroactive ions were estimated, depending on the ZrO2 content in the melts under study. The results obtained were used for electrolysis tests. A new method for Al-Zr master alloys production from oxides during electrolysis of the KF-AlF3Ebased melts was proposed.