A new Zintl phase, Sr 5 In 2 Bi 6 , has been synthesized by solid-state reactions of the corresponding elements in a stoichiometric ratio in welded niobium tube at 750°C. Its structure was established by single-crystal X-ray diffraction. Sr 5 In 2 Bi 6 crystallizes in the orthorhombic space group Pbam (No. 55) with cell parameters of a=24.4500(3), b=7.8800(8), c=4.7400(5)Å and V=913.2(2)Å 3 . It belongs to the Ca 5 Al 2 Bi 6 structure type and its structure features one-dimensional anionic double chains of [In 2 Bi 6 ] 10− with the Sr 2+ ions as spacers. Within the double anionic chain, the In atom is four-bonded by four Bi atoms in a tetrahedral geometry, and these InBi 4 tetrahedra are interconnected into a 1D chain via corner-sharing, each pair of such chains are further condensed into a double chain via Bi–Bi bonds. Results of extended Hückel band structure calculations indicate that Sr 5 In 2 Bi 6 is a semiconductor with a band gap of ∼1.5eV. Sr 5 In 2 Bi 6 is diamagnetic based on magnetic property measurements.