The diruthenium(III) compound [(μ‐oxa){Ru(acac)2}2] [1, oxa2−=oxamidato(2−), acac−=2,4‐pentanedionato] exhibits an S=1 ground state with antiferromagnetic spin‐spin coupling (J=−40 cm−1). The molecular structure in the crystal of 1⋅2 C7H8 revealed an intramolecular metal–metal distance of 5.433 Å and a notable asymmetry within the bridging ligand. Cyclic voltammetry and spectroelectrochemistry (EPR, UV/Vis/NIR) of the two‐step reduction and of the two‐step oxidation (irreversible second step) produced monocation and monoanion intermediates (Kc=105.9) with broad NIR absorption bands (ε ca. 2000 M−1 cm−1) and maxima at 1800 (1−) and 1500 nm (1+). TD‐DFT calculations support a RuIIIRuII formulation for 1− with a doublet ground state. The 1+ ion (RuIVRuIII) was calculated with an S=3/2 ground state and the doublet state higher in energy (ΔE=694.6 cm−1). The Mulliken spin density calculations showed little participation of the ligand bridge in the spin accommodation for all paramagnetic species [(μ‐oxa){Ru(acac)2}2]n, n=+1, 0, −1, and, accordingly, the NIR absorptions were identified as metal‐to‐metal (intervalence) charge transfers. Whereas only one such NIR band was observed for the RuIIIRuII (4d5/4d6) system 1−, the RuIVRuIII (4d4/4d5) form 1+ exhibited extended absorbance over the UV/Vis/NIR range.