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¹H and ¹⁹F spin-lattice relaxation experiments have been performed for a series of ionic liquids sharing the same anion: bis(trifluoromethanesulfonyl)imide but including cations of different alkyl chain lengths: butyltriethylammonium, triethyloctylammonium, dodecyltriethylammo-nium and hexadecyltriethylammonium. The studies have been carried out in the temperature range from 383 to 108 K at the resonance frequency of 200 MHz (for ¹H). A quantitative analysis of the relaxation data has revealed two dynamical processes for both kinds of ions. The dynamics have been successfully modeled in terms of the Arrhenius law. The timescales of the dynamical processes and their temperature evolution have been discussed in detail, depending on the structure of the cation.