Complexes of MX₃ (M = As, Sb or Bi; X = C1, Br or I) with the phosphine and arsine ligands oC₆H₄(ER₂)_2, EMe₃ and MeC(CH₂AsMe₂)₃ (E = P or As, R = Me or Ph) were synthesised and characterised by ¹H- and ³¹P{^-H}-NMR and IR spectroscopy, microanalysis and X-ray crystallography. Most of the structurally characterized [MX₃{o-C₆H₄(ER₂)₂}] complexes adopt a m²halide bridged M₂X₆ dimer structure, with the bridge comprised of primary and secondary M-X bonds, and the ligand bound cis. The [AsC1₃(PMe₃)] complex forms a weakly associated chain polymer in the solid state, comprised of planar As₂C1₆ dimer units with axial, mutually anti PMe₃ ligands. Complexes of SbX₃(X = C1, Br or I) with the chalcogenoethers MeE(CH₂)_nEMe (E = S or Se, n = 2 or 3) were prepared and characterised by ¹H-NMR, IR and microanalysis. X-ray diffraction studies upon a number of examples revealed a diverse array of extended structures. The [SbX₃{MeS(CH₂)_nSMe}] (X = C1, n = 2; X = Br, n = 3) adducts exist as three-dimensional networks and display an unusual mixed bridging/terminal thioether bonding mode. The [SbC1₃{MeSe(CH₂)₃SeMe] complex adopts a one-dimensional chain comprised of Sb₂C1₆ dimers linked by bridging MeSe(CH₂)₃SeMe ligands. Complexes of SbX₃ with the thiacrowns [N]aneS₄ (X = C1, Br; N = 12, 14 or 16) were characterised as above. All were of 1:1 stoichiometry except for the structurally characterised [(SbBr₃)₂([14]aneS₄}] species which displayed a two-dimensional sheet structure comprised of Sb₂Br₆ units linked by the macrocycle. Complexes of AsX₃ (X = C1, Br or I) with MeE(CH₂)_nEMe (E = S or Se, n = 2 or 3, [9]aneS₃ [14]aneS₄ (X = C1 only), [8]aneSe₂ (X = C1, Br), [16]aneSe₄ (X = C1, Br) and [24]aneSe₆ (X = C1, Br) were synthesised and characterised as above. [AsX₃{MeS(CH₂)₂SMe}] (X = Br, I) exist as discrete dimeric molecules similar to the [MX₃{oC₆H₄(ER₂)₂}] complexes, while [AsC1₃([9]aneS₃)] consists of an AsC1₃ unit face-capped by the ligand.