A series of eight tris-arylthiotriazines were synthesized to study the lone pair–π interaction between the triazine ring centroid of these molecules and halogenated solvents. All the eight compounds were characterized using ¹H and ¹³C NMR spectroscopy and single crystal X-ray diffraction techniques. All these compounds show interesting structural properties in the solid state. Unprecedented Janus head type lp⋯π⋯lp and S⋯F⋯S interactions were observed between one of the tris-arylthiotriazines and hexafluorobenzene.