Five bis(ethylenediamine) metal perchlorate (BEMP) complexes like [M(en)(2)](ClO4)(2) (where M = Mn, Co, Ni, Cu, Zn and en ethylenediamine) have been prepared and characterized by gravimetric methods, infrared spectroscopy (IR) and elemental analysis. Thermal decomposition studies have been undertaken using simultaneous thermogravimetry (TG) and differential thermal analysis (DTA) in nitrogen atmosphere. Non-isothermal TG and DTA studies have also been carried out separately in air to examine the effect of atmosphere on thermolysis of these complexes. Thermal stability of the complexes was found to decrease in the order: [Zn(en)(2)](ClO4)(2) > [Mn(en)(2)](ClO4)(2) > [Ni(en)(2)](ClO4)(2) > [Cu(en)(2)](ClO4)(2) > [Co(en)(2)](ClO4)(2).Isothermal TG over the temperature range of decomposition of all these complexes, has been done to evaluate the kinetics of decomposition. Both model fitting and model free isoconversional methods have been used to analyse the kinetics. Isoconversional method has been found to be superior over the conventional model fitting method and is able to describe the complex decomposition of these complexes. It indicates that the values of activation energy vary with the extent of conversion (alpha) while model fitting method results in a single value of E for overall decomposition process which cannot be attributed to any process under such a complex decomposition reaction. Explosion delay (D-E) measurement has been carried out to investigate the response of these complexes under the condition of rapid heating. (C) 2003 Elsevier B.V. All rights reserved.