We report synthesis, crystal and electronic structure, and transport properties of new intermetallic compound ReGa0.4Ge0.6, which was obtained by two-step ampule method from the elements. ReGa0.4Ge0.6 crystallizes in its own structure type (space group I4/mmm, a = 2.89222(3) A, c = 15.1663(3) A, and Z = 4) which can be described as a sequential alternation of blocks of rhenium atoms and blocks of gallium and germanium atoms. Chemical bonding analysis reveals pronounced covalency of Re–Re, Re–E, and E–E (E = Ga and Ge) interactions and an interesting bonding pattern that includes many variations of localized bonding within a single compound, including pairwise homo- and heterometallic bonding, three-centered homometallic and four-centered bonding, and possibly even more delocalized bonding, which is not often encountered in such a simple intermetallic compound. Metallic behavior is confirmed by electronic structure calculations and by measurements of electrical resistivity.