Phase transitions, thermal stability, thermokinetics and activation parameters of degradation reaction of the dicationic ionic liquids (ILs), 1,n-bis(3-methylimidazolium-1-yl)alkane ([BisAlk(MIM) 2 ][2Br]) and monocationic ILs, 1-(3-methylimidazolium-1-yl)alkane ([Alk(MIM)] [Br]), where Alk = Dec, DoDec, TetDec, (decane, dodecane, tetradecane) were evaluated. The influence of an additional cationic head and the alkyl chain length in thermal parameters were also evaluated. The dicationic ILs are more stable than monocationic and thermal degradation of ILs mono-and dicationic did not show linear dependence on the alkyl chain length. Thermokinetic parameters indicated degradation in multiple steps. The monocationic ILs showed a more persistent crystalline phase than dicationic IL, which became totally amorphous after heating. The estimate temperature decomposition, activation energy and thermal transitions enable the determination of which types of ILs are applicable for specific purposes, such as lubricants or solvents at high temperatures, while maintaining ILs physical and chemical properties.