Six dimethylanilinium chlorides (DMACI) have been prepared and characterised. Thermal decomposition of these salts have been studied by TG and DSC techniques. Kinetic parameters have been evaluated from the isothermal and nonisothermal TG data, Contracting area, Contracting cube and Coats-Redfern equations have been found to give the best fits. The decomposition pathways have also been suggested. It has been observed that simultaneous sublimation/decomposition processes are involved during the thermal decomposition of DMACl.