Solid state structures of five new molecular complexes of SbI3 with Py have been determined by single crystal X‐ray structural analysis. In all complexes, all antimony atoms adopt a pseudo‐octahedral coordination geometry, which is completed by additional Sb···I contacts shorter than sum of van der Waals radii, with I‐Sb···I angles close to 180º. Analysis of the electrostatic potentials, the orbital interactions and topological analysis indicate that these contacts are due to the presence of Sb···I pnictogen bonds. The first example of triple pnictogen bond of SbI3 is reported.