The electrochemical and UV-visible spectroscopic and spectroelectrochemical behavior of rhenium(IV), added as K2ReCl6, and the metal-metal bonded rhenium(III) complexes, [Bu(4)N]2Re2Cl8 and Re3Cl9, was studied in the AlCl3-NaClsat melt at 175 degrees C. In the initial voltammograms of solutions containing [ReCl6](2-) a new wave grows in at a potential more positive than the [ReCl6](2-) reduction. The resulting voltammogram, consisting of three reduction and two oxidation waves, does not change further. Spectroelectrochemical results indicate that this first reduction is due to the [ReCl9](2-)/[Re2Cl8](2-) couple. The second wave is believed to be due to the reductions of both [ReCl6](2-) and [Re2Cl8](2-). The results are complicated by the instability of the intermediates as well as the disproportionation of Re3Cl9 to [ReCl6](2-) and rhenium metal.