Cadmium(II) complexes with thiolate ligands have received considerable attention because of their intriguing structural features and relevance to metalloproteins. In this study, a new cadmium(II)–rhodium(III) trinuclear complex, [Cd{Rh(apt)3}2]Br2·4H2O (1, apt = 3-aminopropanethiolate), was synthesized by the reaction of fac-[Rh(apt)3] with cadmium bromide. Compound 1 was characterized using elemental analysis, X-ray fluorescence and IR spectroscopies, and powder X-ray diffraction study. Single-crystal X-ray analysis revealed that the cadmium(II) center in 1 was surrounded by six thiolato S atoms from two fac-[Rh(apt)3] units.