The bis(hydroxamato)oxovanadium(IV) complexes of composition [VO(IAH)2)] (I), [VO(IBH)2)] (II) and [VO(ICH)2)] (III) (where IAH = indole-3-acetohydroxamate; (C9H8NCONHO−); IBH = indole-3-butyrohydroxamate; (C11H12NCONHO−); ICH = indole-2-carbohydroxamate; (C8H6NCONHO−)) synthesized form the reactions of VOSO4·5H2O with bi-molar amounts of potassium salts of the respective hydroxamic acids in methanol have been characterised by elemental analyses, magnetic moment measurements and IR spectral studies. The thermal behaviour of complexes has been studied by TG and DTA techniques. Thermograms indicated that all complexes decompose in two steps yielding [VO(IAH)], [VO(IBH)] and [VO(ICH)] as intermediate of respective complexes and VO2 as the final product of decomposition in each case. From the initial decomposition temperatures (IDT), the order of thermal stability for the complexes has been inferred as II > I > III.