The main goal of this work was to investigate the self-assembly process for water solutions of two gemini surfactants, which differ in spacer chain length, at wide range of temperatures. For this reason the aqueous solutions of hexylene-1,6-bis(dimethyl-octylammonium bromide) and dodecylene-1,12-bis(dimethyloctylammonium bromide) have been examined by the calorimetric (DSC) and densimetric methods within the 293-323 K and 288-323 K temperature range, respectively. The analysis of c(p) values obtained for the examined systems allowed to propose an alternative way to estimate the region where micellization process can occur. The observed temperature dependence of the c.m.c. for surfactants investigated shows a typical shape for ionic gemini surfactants. This behavior was explained as a resultant of two competing effect: decrease in the hydrophilic properties of the surfactant molecule and decrease in the hydrophobic hydration of the alkyl chain along with the temperature increase. The enthalpy of micellization Delta H-mic and other thermodynamics parameters associated with the micellization process: Delta G(mic), Delta S-mic and Delta C-p mic were calculated on the base of the pseudo-phase separation model. As expected, more exothermic enthalpies of micellization are observed with increasing temperature for both the surfactants investigated in this work. (C) 2013 Elsevier B.V. All rights reserved.