In this work, the thermal behavior and heat capacities of four pyridinium and two imidazolium-based ionic liquids (1-ethyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide, C(2)MpyNTf(2), 3-methyl-1-propylpyridinium bis(trifluoromethylsulfonyl)imide, C(3)MpyNTf(2), 1-butyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide, C(4)MpyNTf(2), 1-butyl-3-methylpyridinium trifluoromethanesulfonate, C(4)MpyTFO, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, C(4)MimTFO, and 1-butyl-3-methylimidazolium dicyanamide, C(4)MimDCA) have been experimentally determined using differential scanning calorimetry, and the obtained results have been compared and analyzed. The influence of the scan rate on the thermal analysis has been discussed along with the influence of the structure of the ionic liquid on the heat capacity. (c) 2013 Elsevier B.V. All rights reserved.