Reactions of acyclic and cyclic organotellurium (IV) compounds [R 2TeI 2 {R 2 = (C 2H 5) 2, (n-C 3H 7) 2, C 5H 10}] with the silver salt of carboxylic acids and sodium diethyldithiocarbamate form the organotellurium (IV) complexes (C 2H 5) 2Te(4-NO 2C 6H 4OCO) 2 (1), (C 2H 5) 2Te(C 6H 5CHCHOCO) 2 (2), (n-C 3H 7) 2Te(C 6H 5OCO) 2 (3), (n-C 3H 7) 2Te(4-NO 2C 6H 4OCO) 2 (4), (n-C 3H 7) 2Te(3,5-NO 2C 6H 3OCO) 2 (5), (n-C 3H 7) 2Te(4-OCH 3C 6H 4OCO) 2 (6), (n-C 3H 7) 2Te(C 6H 5CHCHOCO) 2 (7), C 5H 10Te(C 6H 5CHCHOCO) 2 (8) and C 5H 10TeCl[SCSN- (C 2H 5) 2] (9). The X-ray structures of some of these organotellurium (IV) derivatives indicate that they possess ψTBP geometry and dimeric and tetrameric supramolecular associations are achieved through cooperative participation of inter- and/or intramolecular Te⋯O secondary bonds and/or C-H⋯O hydrogen bonds. The intramolecular Te⋯O secondary bond lengths seem to be dependent on the cis- and trans-position placements of free oxygens of the carboxylate groups. It is found that the third-order non-linear optical susceptibilities (χ (3)) of these complexes are in the range 7.21-8.20 × 10 -14 esu and the second order hyperpolarizabilities (γ) are in the range 4.89-5.56 × 10 -32 esu. The presence of the telluracyclopentane (C 5H 10Te) cyclic organic group and cinnamate (C 6H 5CHCHOCO)/diethyldithiocarbamate (SCSN(C 2H 5) 2) ligands having conjugation in the organotellurium (IV) derivatives (8 and 9), appears to be responsible for the higher χ (3) and γ values. © 2012 Elsevier Ltd. All rights reserved.