Catena-poly[fac-triiodobismuth(III)-tris-(µ-ethane-1,2-diylbis(diphenylphosphane oxide-κ2O,O′))], a 2-D sheet network of BiI3 was synthesized from BiI3 and ethane-1,2-diylbis(diphenylphosphane oxide) (DppeO2) in tetrahydrofuran. The crystal structure revealed a trigonal structure with three-fold symmetry at Bi. Bismuth centers show fac-BiI3O3 coordination, with Bi–I = 2.9416(2) Å and Bi–O = 2.4583(17) Å. The I–Bi–I and O–Bi–O angles (95.520(7)° and 79.04(6)°, respectively) indicate trigonal distortion in the Bi octahedron. Bridging DppeO2 ligands centered on inversion centers give rise to a 2-D sheet polymer. The 8.3 Å thick sheets consist of three layers in a sandwich structure. The outer layers are composed of phenyl rings and BiI3 groups with the iodide atoms pointing outward. The central layer consists of the O=PCH2CH2P=O bridging groups. Computational results suggest that semi-conducting behavior arises from Bi(III) centers. A halide to DppeO2 π* transition is suggested by theoretical results.