The dithiocarbamato complexes of oxovanadium(IV), abbreviated as VO(L)2(H2O) where LK are potassium salts of dithiocarbamic acids derived from different substituted aminothiadiazoles, were prepared and characterized by elemental analyses, electrical conductance and magnetic susceptibility measurements, and spectral (electronic and IR) studies. The thermal behaviour of these compounds in non-isothermal conditions was investigated using TG, DTG and DSC techniques. The intermediates obtained at the end of various thermal decomposition steps were identified from elemental analyses and infrared spectral studies. The graphical method of Coats and Redfern was employed to evaluate the kinetic parameters such as the apparent activation energy and order of reaction. The heats of reaction for the different decomposition steps were calculated from the DSC curves.