Electrochemical preparation of different phases Al–Y alloys were investigated in LiCl–KCl–AlCl3–Y2O3 melts at 773 K by cyclic voltammetry, square wave voltammetry, open circuit chronopotentiometry, and polarization curve. These electrochemical measurements showed that the underpotential deposition (UPD) of yttrium on pre-deposited Al forms two Al–Y intermetallic compounds. The results of X-ray diffraction (XRD) analysis indicate that the two differrent Al–Y intermetallic compounds are Al2Y and α-Al3Y. The microstructure and micro-zone chemical analysis of Al–Y alloys were characterized by scanning electron microscopy (SEM) and energy dispersive spectrometry (EDS), respectively. The results illustrate that element Y mainly distributes on nubby precipitates. Different phases Al–Y Alloys can be obtained by adjusting the concentration of AlCl3.