Dirhodium acetate di(cyclohexylisocyanide) [Rh2(O2CCH3)4(C≡NCy)2] is prepared by treating Rh2(OAc)4 with cyclohexylisocyanide. The crystal structure of [Rh2(O2CCH3)4(C≡NCy)2] is determined by a single crystal X-ray diffraction (XRD) analysis. The title compound crystallizes in the orthorhombic system (space group Ibam). According to the single crystal XRD analysis data, the Rh atom exhibits a slightly distorted octahedral coordination geometry. The Rh1—Rh1—C1 fragment is almost linear (177.87°); ORhO angles are 88.28°, 88.79°, and 91.25°. In addition, the structure of the title compound is unambiguously confirmed by the aggregation of elemental analysis (C, H, N), ESI+—MS, and IR spectroscopy data.