Cyclic voltammogram and square wave voltammograms indicated that Cu (II) ion being reduced to Cu(0) was a two-electron process: Cu(II) + e− → Cu(I) and Cu(I) + e− → Cu(0). The diffusion activation energy for Cu (I) ions was calculated as 42.85 kJ mol−1. The equilibrium potential and apparent standard potential for Cu (I)/Cu(0) redox couple was measured by open circuit chronopotentiometry at a temperature of 773–923 K. Three reduction peaks, corresponding to the formation of PrxCuy intermetallic compounds, were detected from cyclic voltammogram and square wave voltammogram obtained by co-reduction of Pr (III) and Cu (II) or electrodeposition of Pr (III) on Cu electrode. Furthermore, potentiostatic electrolysis was performed to extract the element Pr on Cu electrode, and the electrolytic products were analyzed by scanning electron microscopy equipped with energy dispersive spectrometry. Meanwhile, the highest extraction efficiency of Pr (III) ions could reach about 99.81% at − 2.20 V for 22 h at 823 K.