Kinetics of the aluminum and scandium electrodeposition from the oxide-fluoride and fluoride melts was studied by mean of voltammetry. The parameters (potential range, currents) of aluminum and scandium electrodeposition from the fluoride melts with the additions of Al2O3, Sc2O3, AlF3, and ScF3 in the temperature range of 750–800°С were defined. A novel approach has been proposed to produce the Al–Sc master alloys enriched with scandium, including the electrodeposition of aluminum and scandium on a solid cathode during the electrolysis of oxide-fluoride or fluoride melts and the subsequent dissolution of the obtained cathode sediment in liquid aluminum. On the basis of electrochemical measurements, the parameters of stable electrolysis of the melts under study were chosen and electrolysis tests were carried out to produce Al-Sc master alloys. The cathode current efficiencies during the co-electrodeposition of aluminum and scandium were estimated, and the microstructure of the obtained Al–Sc master alloys was studied.