We here report on the conformational evolution of the bis(trifluoromethanesulfonyl)imide anion (TFSI−) in protic and aprotic TFSI−-based ionic liquids as a function of temperature. The investigation is performed by Raman spectroscopy in the spectral ranges 240-380 cm−1 and 715-765 cm−1, where the interference from bands due to the cations is negligible. The contribution from each TFSI− conformation, i.e. the cisoid (C1) and the transoid (C2), is quantified in order to estimate the enthalpy of conformational change, ΔH, which is found to be in the range 3.4–7.3 kJ/mol in the liquid state. Conformational information is for the first time determined from the 740 cm−1 band, which previously mainly has been used as an indicator of ion-ion interactions. The similarity in ΔH values obtained from the two spectral ranges demonstrates the validity of using also the 740 cm−1 band for the quantification of the TFSI conformational evolution. Copyright © 2010 John Wiley & Sons, Ltd.