Mixed-ligand complexes Cd(2,2′-Bipy)(i-PrOCS2)2 (I) and Cd(2,2′-Bipy)(i-BuOCS2)2 (II) have been prepared. Their structures were solved using the X-ray diffraction technique (X8 APEX diffractometer, MoK α radiation, 1941 and 4244 F hkl , R = 0.0188 and 0.0379). The crystals are orthorhombic with unit cell parameters a = 18.1404(4) Å, b = 6.9513(1) Å, c = 17.5835(4) Å; V = 2217.27(8) Å3, Z = 4, space group Pccn (for complex I) and a = 11.7890(3) Å, b = 12.1859(3) Å, c = 17.5335(5) Å; V = 2518.9(1) Å3, Z = 4, space group P212121 (for complex II). The structures consist of isolated mononuclear molecules. The cadmium atoms have distorted octahedral N2S4 environments. Molecular packings and intermolecular interactions in the structures are considered.