The structure of the previously reported complex bis(μ-naphthalene-2-thiolato-κS:S)bis(tricarbonyliron)(Fe-Fe), [Fe(CHS)(CO)], has been characterized by X-ray diffraction. In the solid state, the dinuclear complex adopts a butterfly-like shape, with an equatorial-axial spatial orientation of the naphthalene groups covalently coupled to the [SFe(CO)] unit. The asymmetric unit contains three independent [(μ-naphthalene-2-thiolato)Fe(CO)] molecules. These molecules show intermolecular π-π stacking interactions between the naphthalene rings, which was confirmed by Hirshfield surface analysis. The electronic spectrum of the complex recorded in acetonitrile shows a band centered at 350 nm (ℇ = 4.6 × 10 M cm) and tailing into the visible region. This absorption can be attributed to a π→π* electronic transition within the naphthalene moiety and a metal-based d→d transition.