Abstract Besides the previously known α-form (monoclinic, P2₁/c, Z=4) of bis(2,6-dimesitylphenyl)ditelluride, two new polymorphic modifications, namely the β-form (monoclinic, P2₁/c, Z=8) and the γ-form (triclinic, P1̅, Z=2), were obtained serendipitously during chemical reactions. In all three modifications, the individual molecules possess significantly different conformations and bond parameters, such as Te–Te bond lengths, C–Te–Te bond angles, C–Te–Te–C torsion angles and intramolecular Menshutkin interactions, which is also reflected in their non-covalent interactions with adjacent molecules in the crystal lattice via London dispersion and electrostatic forces. The interplay between intermolecular and intramolecular forces in these conformational polymorphs was investigated using quantum chemical calculations, which reveal that the β-form should be thermodynamically stable at absolute zero. In contrast, crystallization experiments and thermoanalytical investigations indicate that the α-form is stable at high temperatures and therefore, both forms might be related by enantiotropism.