The electrochemical and UV-visibie spectroscopic and spectroelectrochemical behavior of rhenium(IV), added as K~ReCI~, and the metal-metal bonded rhenium(III) complexes, [Bu~N]~Re~CI~ and Re~CI~, was studied in the A1C13-NaClsa t melt at 175~ In the initial voltammograms of solutions containing [ReCl~] 2-a new wave grows in at a potential more positive than the [ReC16] ~-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 [ReCI~]~-/[Re2CI~] ~-couple. The second wave is believed to be due to the reductions of both [ReCI~] 2-and [Re2CI~] 2-. The results are complicated by the instability of the intermediates as well as the disproportionation of Re, C1, to [ReCI~] ~-and rhenium metal.