In resent years, the studies on the self-assembly process of micelle for gemini surfactants have made significant progress. However, most studies on the thermodynamic properties of micellization concentrate on establishing the relationship between ΔG_mic and cmc, and there are directly few calorimetric results. Thus, the detailed driving forces involved in the self-assembly process of these surfactants cannot be recognized. To understand energetically the mechanism and the entropy-enthalpy compensation in micellization process of the cationic surfactants and to elucidate the relationship between molecular structures and macroscopically thermodynamic properties, we have made microcalorimetric measurements on the series of cationic surfactants. We will review our research work in recent years and address to other related literatures on the thermodynamics of micellization of the series of gemini surfactants in aqueous solution.