The chalcogen bonding (ChB) ability of Te is studied in symmetrical diaryl ditellurides ArTeTeAr. Among the two Te σ‐holes, the one along the less polarized Te−Te bond was calculated as the more electropositive. This counter‐intuitive situation is due to the hyperconjugation contribution from Te lone pair to the σ* of the adjacent Te which coincides with σ‐hole along the more polarized Te−Ar bond. ArTeTeAr showed notable structural features in the solid state as a result of intermolecular Te⋅⋅⋅Te ChB, such as a Te 4 rectangle through dimer aggregation or a triangular Te 3 motif, where one Te interacts with both Te atoms of a neighboring molecule through both its σ‐hole and lone pair, in a slightly frustrated geometry. Lewis acidity of ArTeTeAr was also evaluated by NMR with R 3PO as σ‐hole acceptors in different solvents. Thus, 125Te NMR allowed monitoring Te⋅⋅⋅O interaction and delivering association constants ( K a) for 1 : 1 adducts. The highest value of K a=90 M −1 was measured for the adduct between ArTeTeAr bearing CF 3 groups and Et 3PO in cyclohexane. Notably, by using nBu 3PO, Te⋅⋅⋅O interaction was revealed by 19F‐ 1H HOESY showing spatial proximity between CF 3 and CH 3 of nBu 3PO.