A new bismuth(III) chloride complex with 1-methyl-2(3 H)-imidazolethione ( meimtH) has been synthesized and characterized via standard methods including solid state 13C nuclear magnetic resonance (NMR) and single crystal X-ray diffractometry. The complex, BiCl 3[ meimtH] 2.5 · H 2O, crystallizes in a triclinic space group. The complex has two different coordination spheres for bismuth, which are linked together in the solid state via hydrogen bonding. One coordination sphere is distorted octahedral with the ligands in meridional positions, while the other is a dimer consisting of two octahedra sharing a common edge through bridging chlorine atoms. The ligands are cis to each other and trans to the chlorine bridges, while the remaining four chlorine atoms are trans to each other and perpendicular to the chlorine–sulfur plane. There is no strong evidence for a stereoactive lone pair in either coordination sphere.