The thermal stability of an ionic liquid (IL) is an important parameter and limits the maximum operation temperature. However, the definition of stability and of the maximum operation temperature, respectively, is still an open question. Typically, non-isothermal thermogravimetrical analysis (TGA) is used to determine the stability, which is then mostly defined by the onset temperature, i.e. by the temperature where a certain mass loss of e.g. 1% is reached. Unfortunately, the rate of mass loss depends on the apparatus and conditions (e.g. heating rate), and may be governed by evaporation or by thermal decomposition or by a combination of both. In this work, isothermal as well as non-isothermal TG/DTG measurements at different heating rates were used as basis to model the combined kinetics of evaporation and decomposition, thereby taking 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [BMIM][BTA] as an example. The measured and predicted mass losses are in good agreement, and the simulation of TG/DTG experiments by the methods outlined in this work leads to a reliable estimation of the evaporation (as shown by comparison with literature data) as well as of the decomposition rate. For a closed system, where the mass loss by evaporation is negligible, a novel criterion (1% mass loss by thermal decomposition within one year) is presented to estimate the maximum operation temperature of ILs.