The reaction of organo(heterocyclic)tellurium(IV) derivative: C 8H 8TeI 2(1,3-dihydro-2 λ 4-benzotellurole-2,2-diyl diiodide) with NH 4S 2CNC 5H 10 (ammonium piperidine dithiocarbamate) gives C 8H 8Te(S 2CNC 5H 10) 2 ( 1) and Te(S 2CNC 5H 10) 2 ( 2) or C 8H 8TeI(S 2CNC 5H 10) ( 5) according to the reaction conditions. In such type of metathetical reactions, the formation of 2 is unprecedented and it corresponds to the first Te–C cleaved product. The reaction of 2 with CH 3I, yields the oxidative addition product, CH 3TeI(S 2CNC 5H 10) 2 ( 8). The formation of 2 is also supported through Quantum Chemical calculations. Another Te–C bond cleaved product TeI 2[(C 13H 10N 2S) 2] · 4C 4H 8TeI 2 ( 9) is obtained in the reaction of C 4H 8TeI 2 (1,1,2,3,4,5-hexahydro-1,1-diiodotellurophene) with NH 4S 2CNHC 6H 5 (ammonium aniline dithiocarbamate). The reaction of 1,1,2,3,4,5,6-heptahydro-1-iodo-1-(morpholine dithiocarbamato) tellurane [C 5H 10TeI(S 2CNC 4H 8O)] ( 10) with 1,10-phenanthroline gives an unusual product C 12H 8N 2 · C 4H 10INO ( 11). The structures of the new complexes 2, 8, 9, 10 and 11 have been determined by the X-ray analysis.