Two tetraorganoditelluroxane diiodides (R 2 Te) 2 OI 2 (3, R=p-MeOC 6 H 4 ; 5, R=Me) were prepared by the reaction of (p-MeOC 6 H 4 ) 2 TeI 2 (1) and (p-MeOC 6 H 4 ) 2 TeO (2) and the base hydrolysis of Me 2 TeI 2 (4), respectively. The base hydrolysis of C 4 H 8 TeI 2 (8) afforded the tritelluroxane diiodide (C 4 H 8 Te) 3 O 2 I 2 (9). The reaction of Me 2 TeI 2 (4) and Me 2 Te(OH) 2 (6) in a ratio of 1:3 produced the coordination polymer of the composition 2 (Me 2 Te) 2 O(I)OH·H 2 O (7). An attempt at preparing an adduct of 3 with iodine failed but provided co-crystals of (p-MeOC 6 H 4 ) 2 TeI 2 ·12I 2 (1a). The supramolecular structures of 1a, 3, 5, 7 and 9 are dominated by structurally directing secondary Te⋯I interactions.