The new compound (NEt 4 )[(acac) 2 RuS 2 ReS 2 Ru(acac) 2 ] was characterized by cyclic voltammetry to reveal reversible reduction and oxidation behavior. While the redox products proved EPR silent, the UV–Vis-NIR spectroelectrochemistry showed shifted charge-transfer absorptions and a typical near-infrared intervalence (Ru II →Ru III ) band at λ max =1725nm (ε=1800M −1 cm −1 ) for the one-electron oxidized intermediate. The results are discussed in comparison to those obtained for [(bpy) 2 RuS 2 ReS 2 Ru(bpy) 2 ]Cl 3 .