Al-Ti-Ce master alloy was prepared by aluminothermic reduction of TiO2 and CeO2 in Na3AlF6-NaCl-KCl electrolytic system. The effects of reaction time, reaction temperature, electrolytic composition (mass percent of Na3AlF6) and K2TiF6 dosage on the phase structure and chemical composition of Al-Ti-Ce master alloy were studied, respectively. The experimental results show that there are only three phases in the Al-Ti-Ce master alloy, which are ɑ-Al, Al3Ti and Ti2Al20Ce, at the range of process parameters used in each experiment, and the optimal single-factor parameters in preparing Al-Ti-Ce master alloy by aluminothermic reduction are as follows: reaction time 90 min, reaction temperature 850 ℃, mass percent of Na3AlF6 40 wt%, K2TiF6 dosage 20 mol%. The results of thermodynamic analysis further show that the main several chemical reactions proposed in this study are feasible on the checked experimental conditions.