The electrochemical reaction of Bi(III) and co-reduction behaviour of Bi(III) and Y(III) ions were researched in molten LiCl-KCl on a tungsten(W) electrode employing a range of electrochemical techniques. Cyclic voltammetric and square-wave voltammetric results revealed that the reduction of Bi(III) was a one-step process, with the exchange of three electrons on a W electrode, and diffusion-controlled. The electrochemical curves showed two reduction peaks pertaining to the formation of Bi-Y alloy compounds, because of the co-reduction of Bi(III) and Y(III) by metallic Y deposited on the pre-deposited Bi-coated W electrode and reacting with Bi metal in molten LiCl-KCl. Furthermore, galvanostatic electrolysis was conducted using liquid Bi as cathode to extract yttrium at different current intensities, and the extractive products were analyzed by SEM, EDS and XRD. The results indicated that BiY intermetallic compound was formed in the molten LiCl-KCl-YCl3 system.