The polymeric compounds {Cd(bix)[(CH3O)2PS2]2} n (1) and {Cd(bix)[(C2H5O)2PS2]2} n (2) [bix = 1,4-bis(imidazole-l-ylmethyl)benzene; (CH3O)2PS2 = O,O′-dimethyldithiophosphate; (C2H5O)2PS2 = O,O′-diethyldithiophosphate] have been synthesized and characterized by single-crystal structure determinations, elemental analyses, and IR spectra. X-ray diffraction studies revealed that they exhibit one-dimensional polymeric structures with a zigzag chain for 1 and a linear chain for 2, connected by π–π stacking interactions to form 2D networks. Their solid-state luminescent properties were also studied. Crystal data for 1 at −100°C: monoclinic, space group C2/c, a = 18.5196(7), b = 10.2337(3), c = 14.0241(11) Å, β = 90.190(2)°, Z = 4, R 1 = 0.0362; for 2 at −100°C: triclinic, space group , a = 8.9837(10), b = 9.5038(0), c = 10.4893(0) Å, α = 65.706(9), β = 77.856(10), γ = 73.184(10)°, Z = 1, R 1 = 0.0316.