The separation of Re(VII) and V(V) by solvent extraction with TBP was investigated by varying the HCl, metal and chloride ion concentrations. Re(VII) was selectively extracted over V(V) from the HCl solution. The highest separation between Re(VII) and V(V) occurred at a concentration of 2.0 M HCl. The extraction reaction of Re(VII) by TBP was verified using the slope analysis method. Changing the concentration ratio of the two metals and the chloride ion concentration had little effect on the extraction of V(V). Re(VII) could be completely stripped from the loaded TBP when the pH of the stripping solution was higher than 3.0. The obtained results can be utilized to develop a process for separating Re(VII) and V(V) from HCl solutions