N,N and N,N,N – chelated antimony(III) and bismuth(III) chlorides L1-3MCl2 1 – 4 [for L1: M = Sb (1), for L2: M = Sb (2) and for L3: M = Sb (3) and Bi (4)], containing ligands L1-3 derived from the pyrrole ring (where L1 = C4H3N-2-(CH=N-2´,6´-iPr2C6H3), L2 = C4H2N-2,5-(CH2NMe2)2, L3 = C4H2N-2,5-(CH2NC4H8)2), were prepared by treatment of lithium precursors with SbCl3 or BiCl3. Molecular structure of 1 – 4 was described both in solution (NMR spectroscopy) and in the solid state (single-crystal X-ray diffraction analysis). Structures of 1-4 were also subjected to a density functional theory study.