The work concerned the electrochemical behaviors of Y(Ⅲ) on W and Ni electrodes in molten LiCl-KCl salts by a series of electrochemical techniques. The electrochemical reaction of Y(Ⅲ) to Y(0) proceeded in a one-step reduction process with the exchange of three electrons, Y(Ⅲ)+3e~–→Y(0). Compared with the cyclic voltammogram and square wave voltammogram obtained on W electrode, the reduction potential of Y(Ⅲ) on Ni electrode was observed at less negative potential than the one of Y(Ⅲ) to give pure Y metal on W electrode, which revealed the occurrence of underpotential deposition of Y(Ⅲ) on Ni electrode. Electromotive force(emf) measurements were performed to calculate the relative partial molar Gibbs energies and activities of Y in Y-Ni alloys. The standard Gibbs energies of formation for different Y-Ni intermetallic compounds were also estimated. The different Y-Ni alloys were formed by potentiostatic electrolysis at different potentials and characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM), and energy dispersive spectrometry(EDS). It was found that four intermetallic compounds, YNi_5, Y_2Ni_7, YNi_3 and YNi_2, were selectively produced by controlling applied potential. The work around the electrochemical behaviors of Y (III) on W and Ni electrodes in molten LiCl-KCl salts by a series of electrochemical techniques. The electrochemical reaction of Y (III) to Y (0) proceeded in a one-step reduction process Compared with the cyclic voltammogram and square wave voltammogram obtained on W electrode, the reduction potential of Y (III) on Ni electrode was observed at less negative potential than the one of Y (III) to give pure Y metal on W electrode, which revealed the occurrence of under underposition deposition of Y (III) on Ni electrode. Electromotive force (emf) were measured to calculate the relative partial molar Gibbs The energies and activities of Y in Y-Ni alloys. The standard Gibbs energies of formation for different Y-Ni intermetallic compounds were also estimated. The different Y-Ni alloys were formed by potentiostatic electrolysis at different potentials and characterized by X-ray diff raction (XRD), scanning electron microscopy (SEM), and energy dispersive spectrometry (EDS). It was found that four intermetallic compounds, YNi_5, Y_2Ni_7, YNi_3 and YNi_2, were selectively produced by controlling applied potential.