Our previous simulation studies on the nanostructuration of ionic liquids are extended to the homologous series of trialkylmethylammonium bis(trifluoromethanesulfonyl)amide ionic liquids-[N(1 n n n)][NTf(2)] (n = 4, 6, and 8)-recently studied by Pott and Méléard using small-angle X-ray scattering. Comparisons between experimental and simulation results allowed us to conclude that ionic liquids of this and other homologous series with sufficiently large alkyl side chains are nanostructured media composed by polar and nonpolar domains and that their complex structure can be further subdivided according to different classes of morphology (globular, filamentous, stratified). These different topologies are a result of the specific ionic frames and interactions, characteristics of each type of cation and anion present in the homologous series.