Molecular structures of two new SbCl₃–Py complexes, (SbCl₃)₄Py₄ and (SbCl₃)₃Py₅, in the solid state have been determined by single crystal X-ray diffraction. In both complexes all Sb atoms adopt a pseudo-octahedral coordination geometry which is completed by additional Sb⋯Cl contacts shorter than sum of van der Waals radii, with Cl–Sb⋯Cl angles close to 180°. These contacts indicate the presence of Sb⋯Cl pnictogen bonding. To reveal its nature, the DFT calculations were performed followed by the analyses of the electrostatic potentials, the orbital interactions and topological analysis.