ABSTRACT The stability of 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl) imide (PYR13TFSI), 1-methyl-1-propylpyrrolidinium bis(fluorosulfonyl) imide (PYR13FSI), 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide (PYR14TFSI) and 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide (EMIM TFSI) ionic liquids (ILs) at different temperatures (room temperature and 95°C) was investigated by ion chromatography (IC) hyphenated to a mass spectrometer. The degradation of the cations can be summarized in the following way: The side chain of the main molecule cleaves and reacts subsequently with the main cation molecule to new decomposition products. In addition, the results show that at elevated temperatures more decomposition products are formed. The influence of Li+ cation based electrolyte salts, lithium hexafluorophosphate (LiPF6), lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) and lithium perchlorate (LiClO4), on the decomposition of the ionic liquids was analyzed over a long term stability study at room temperature and 60°C. It was found out that in the mixtures of ILs and electrolyte salt, the same decomposition products were formed like in the pure ILs at the same temperature. Accordingly, there is no influence of the electrolyte salts on the decomposition behavior of the IL cation. The influence of the counter anion on the decomposition of PYR13 + was analyzed as well. It was observed that different decomposition products were detected for PYR13TFSI and PYR13FSI.