The structures of two new molecular complexes of antimony pentafluoride with pyridine (Py) and acetonitrile (AN), SbF₅·Py and Sb₂F₁₀·AN, and a molecular complex of antimony trifluoride Sb₂F₆·Py and its ionic derivative [HPy]⁺[Sb₂F₇]⁻in the solid state have been determined by single crystal X-ray structural analysis. The complexes Sb₂F₁₀·AN and Sb₂F₆·Py are the first structurally characterized compounds of dimeric antimony fluorides. To reveal the nature of bonding in the complexes and their stability, DFT computations of the electronic structure and thermodynamic characteristics were performed, in particular the analysis of the electrostatic potentials, the orbital interactions and the topology. The results indicate that the intermolecular Sb⋯F interactions can be described as a network of pnictogen bonds.