Variable temperature X-ray diffraction has been used to probe the structure and dynamics of the solid adducts of 1,3,5-trimethylbenzene (mesitylene) and hexafluorobenzene. PXRD patterns and DSC traces of near equimolar mixtures reveal two solid-state phase-transitions at 179.2 K and 111.0 K. The crystal structures of all three solid phases of this material have been solved by SXD. In contrast to previous studies on the adduct benzene–hexafluorobenzene, there is pairing of the mesitylene and hexafluorobenzene molecules in all three phases, each consisting of close-packed parallel columns of alternating C6H3(CH3)3 and C6F6 molecules packed face to face in a staggered conformation. Differences in structure between the phases illustrate the subtle interplay of quadrupole versus bond-dipole electrostatic interactions.