1-Dodecyl-2-methylpyridinium bromide ([C 12 -2-Pic][Br]) and 1-hexadecyl-2-methylpyridinium bromide ([C 16 -2-Pic][Br]) are two ionic liquid crystals presenting thermotropic smectic phases above 80 °C. Aiming to take advantage of the liquid crystalline properties at lower temperatures, lyotropic aqueous systems were prepared from these two organic salts. Both systems were characterized by polarized optical microscopy (POM), X-ray powder diffraction (XRD), and fast field cycling nuclear magnetic resonance (FFC-NMR) relaxometry to assess their texture, phase structure, and molecular dynamics, respectively. The mesomorphic behavior was induced at room temperature. Moreover, the lyotropic [C 12 -2-Pic][Br] aq revealed a smectic phase with higher separation between layers, different from the lamellar phases found in the thermotropic system (S 1 and S A ), which is thermally stable up to 50 °C. Furthermore, the surfactant nature of the ionic liquids diluted solutions investigated in this work allowed the formation of foams. It was found that the precursor solutions of the lyotropic dilutions with the longest alkyl chain ([C 16 -2-Pic][Br] aq ) originated liquid foams with more stable structures than those of [C 12 -2-Pic][Br] aq .