Thermal decomposition of tetraethylammonium perchlorate has been studied by thermogravimetry, differential thermal analysis and mass spectrometry. The title compound undergoes crystallographic transformation at 98°C and explodes at 298°C. The heat of phase transformation is calculated to be 2.5 kcal/mol. The mass spectral data suggest that the salt undergoes thermal decomposition into neutral particles which are then vapourized and ionized as well as oxidized. Copyright © 1982 Verlag GmbH & Co. KGaA, Weinheim