A new bismuth(III) iodide inorganic/organic hybrid containing larger heterocyclic conjugated organic ligand, [(dppz)2Bi2I6]·2DMF(1)(dppz = dipyrido[3,2-a:2’,3’-c]phenazine), has been synthesized by solution process and structurally determined by X-ray diffraction method. 1 crystallizes in triclinic, space group P1 with Mr = 1844.08, a = 9.215(5), b = 11.488(6), c = 12.424(9) ?, α = 106.66(2), β = 90.84(2), γ = 92.34(2)°, V = 1258.5(13)?3, Z = 1, Dc = 2.433 g/cm3, F(000) = 830, μ(MoKα) = 10.702 mm–1, the final R = 0.0834 and wR = 0.1947 for 2749 observed reflections with I > 2σ(I). 1 consists of a dimeric structure [(dppz)2Bi2I6], in which two [(dppz)BiI3] fragments are bridged by a pair of iodine atoms. Hydrogen bonds and π···π stacking interactions contribute to the structural extension and stabilization. Experimental band gap of about 2.13 eV indicates its semiconductor nature. The optical absorption spectrum and electronic structure were also discussed. A new bismuth (III) iodide inorganic / organic hybrid containing larger heterocyclic conjugated organic ligand, [(dppz) 2Bi2I6] 2DMF (dppz = dipyrido [3,2- a: 2 ’, 3’-c] , has been synthesized by solution process and structurally determined by X-ray diffraction method. 1 crystallizes in triclinic, space group P1 with Mr = 1844.08, a = 9.215 (5), b = 11.488 (6), c = 12.424 , α = 106.66 (2), β = 90.84 (2), γ = 92.34 (2) °, V = 1258.5 (13)? 3, Z = 1, Dc = 2.433 g / cm3, F , μ (MoKα) = 10.702 mm-1, the final R = 0.0834 and wR = 0.1947 for 2749 observed reflections with I> 2σ (I). 1 consists of a dimeric structure [(dppz) 2Bi2I6] dppz) BiI3] fragments are bridged by a pair of iodine atoms. Hydrogen bonds and π ··· π stacking interactions contribute to the structural extension and stabilization. Experimental band gap of about 2.13 eV indicates its semiconductor nature. The optical absorption spectrum and electronic structure were also discussed.