Thermotropic liquid crystal formation by salt-free catanionic surfactants (alkyltrimethylammonium alkylsulfonates, herein designated as TA(m)So(n)) has been investigated as a function of chain length mismatch (asymmetry). Previous studies on these compounds have revealed an unusual and rich asymmetry-dependent lyotropic phase behavior. Herein, phase transition temperatures and transition enthalpies/entropies were determined by differential scanning calorimetry, while mesophases were assigned by polarized light microscopy. Three series of compounds were investigated, namely: the TA(16)So(n) series, where n = 6-10; the TA(m)So(8) series, where m = 12-16; and a constant m + n series, TA(m)So(n) where m + n = 22. Typically, several solid phases and two smectic mesophases are found prior to isotropization to the liquid phase. As asymmetry decreases, two somewhat counterintuitive tendencies emerge: a general decrease in enthalpy/entropy for solid-solid and solid-first mesophase transitions, and an increase in solid-first mesophase transition temperatures. Yet, solid phases are seen to be more stable for the most asymmetric compounds, while the second mesophase is more stable for the least asymmetric ones, in what appears to be a more complex behavior than expected. The results are globally interpreted in terms of subtle differences in chain interdigitation and packing, and odd-even chain effects. (C) 2013 Elsevier Inc. All rights reserved.