This work highlights the factors tuning the thermal stability of imidazolium-based ionic liquids (IL) associated to bis(trifluoromethanesulfonyl)imide anion [NTf2]. The decomposition temperatures (Td) were evaluated by thermogravimetric analyses (TGA) with optimized parameters to obtain reproducible Td. The impact of the alkyl chain length and of the presence of functional groups and unsaturations on Td were evaluated. The thermal behaviour was governed by Van der Waals interactions between alkyl chains, and by inter and intra coulombic interactions such as hydrogen bonds.