The electrochemical formation of Dy-Ni alloys was investigated in a molten CsCl-DyCl3 system at 973 K under a dry Ar gas atmosphere. Open-circuit potentiometry was performed with a Ni electrode after depositing Dy metal at 0.13 V(vs. Cs+/Cs) for 60 s. Five potential plateaus were observed at 0.34 V, 0.44 V, 0.54 V, 0.79 V and 0.91 V, which were considered to correspond to the potentials of two-phase coexisting states of different Dy–Ni alloys. Potentiostatic electrolysis was conducted at 0.31 V for 4 h and 0.41 V for 1 h using Ni plate electrodes, and XRD analysis indicated the formation of DyNi and DyNi2, respectively. After the formation of DyNi2 on the Ni plate electrodes, potentiostatic electrolysis were also conducted at 075 V and 0.85 V for 1 h. The formed DyNi2 was transformed to Dy2Ni7 and DyNi5 at 0.75 V, while DyNi5 was formed at 0.85 V.