Needle-shaped red crystals of RhSCl5 were obtained by reaction of Rh metall or RhI3 with SCl2 in a closed silica ampoule. In the monoclinic crystal structure the Rh atoms are octahedrally coordinated by 5 Cl atoms and a SCl2 ligand. In each case six RhCl5(SCl2) groups are connected with each other by two common edges of Cl atoms to form hexameric molecules [RhCl3(SCl2)](6). In the pseudohexagonal unit cell (monoclinic, space group C2/c, a = 26.215(5) Angstrom, b = 6.7750(10) Angstrom, c = 26.868(5) Angstrom, beta = 119.06(3)degrees, Z = 4) the molecules are stacked in columns and form a hexagonal rod package.