Synthesis of supramolecular assemblies of organotellurium(IV) dithiocarbamates, formed through intramolecular Te⋯S secondary bonds, intermolecular Te⋯X (X = I, S) secondary bonds and C-H⋯O hydrogen bonds are described. The supramolecular assemblies containing diethyldithiocarbamate group may serve as possible "rescue agents". The third order nonlinear optical susceptibility of the organotellurium(IV) diethyldithiocarbamate C 4H 7(CH 3)Te[S 2CN(C 2H 5) 2] 2 (1) has been studied by degenerate four wave mixing technique using a picosecond laser. It is found to exhibit efficient third-order nonlinear optical susceptibility (χ (3)) of 7.21 × 10 -14 esu and second order hyperpolarizability (γ) of 4.88 × 10 -32 esu. © 2012 Elsevier B.V. All rights reserved.