The reaction of fac-[RuII(CO)3Cl2(N3-MBI)], 1, (MBI = N1-methylbenzimidazole) with HBAL (HBAL, N-benzoyl-dl-alanine) brought about cis-[RuI(CO)2(N3-MBI)(μ2-O,O-BAL)]2, 2. The new binuclear organometallic compound was structurally characterized via X-ray diffraction (XRD, 293 ± 1 K) and FT-IR (KBr matrix) at the solid state, and via 1H-NMR (1·10−2 M, CDCl3) and UV-Vis (8.6·10−5 M, CH3OH) in solution. Simulation of the molecular structure was carried out at DFT-B3LYP/(Ru, Lanl2DZ; CHNO, 6-31G**) level at the gas phase, and structural parameters were compared to experimental (XRD) parameters for 2, and equivalent computations previously performed for the parent mononuclear RuII complex, 1. The absence of any other anionic/cationic molecule either as ligand or co-crystallized species, in addition to the two bridging carboxylato molecules per each dimer molecule was in agreement with the (+1) oxidation state for the two ruthenium centers. The two MBI ligands resulted linked to the metal atoms in trans position with respect to the RuRu bond. The RuRu, and the RuN vectors measure 2.6984(4), and 2.236(4) and 2.183(4) Å, respectively.