N,N- and N,N,N-chelated antimony(III) and bismuth(III) chlorides L(1-3)MCl2 1-4 [for L(1): M = Sb (1), for L(2): M = Sb (2) and for L(3): M = Sb (3) and Bi (4)], containing ligands L(1-3) derived from the pyrrole ring (where L(1) = C4H3N-2-(CH[double bond, length as m-dash]N-2',6'-iPr2C6H3), L(2) = C4H2N-2,5-(CH2NMe2)2, L(3) = C4H2N-2,5-(CH2NC4H8)2), were prepared by the treatment of lithium precursors with SbCl3 or BiCl3. Molecular structures 1-4 of were 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.