This first report on temperature programmed decomposition Of C60Br24 and C60Br6 using evolved gas analysis and mass spectrometry (EGA-MS) in the temperature range 323-523 K revealed multiple decomposition routes. The deconvoluted decomposition profiles with bi- and tri-modal features in C60Br24 and C60Br6, respectively, indicated evolution of interstitial bromines at a higher temperature as compared to the release of bonded bromines. C60Br6, on decomposition yields cyclopentadienyl radical intermediate and the overall process was found to be diffusion-reaction limited with a diffusion coefficient associated with the release of the interstitial bromine as 4.3 x 10(-19) cm(2) s(-1). (C) 2003 Elsevier Science B.V. All rights reserved.