The power-time curves of the micelle formation process were determined for three kinds of quasi-surfactants [lithium di(2-ethyl-hexyl) phosphate, sodium di(2-ethyl-hexyl) phosphate, and potassium di(2-ethyl-hexyl) phosphate] and five kinds of alkanes (octane, decane, dodecane, tetradecane, and hexadecane) with sec-octyl alcohol by titration microcalorimetry. The critical micelle concentration (CMC), aggregation number (n), formation constant of micelle (K), and thermodynamic functions (Delta(r)H(m)(0), Delta(r)G(m)(0), and Delta(r)S(m)(0)) were obtained. For different quasi-surfactants and homologue of the alkanes, the relationships between the carbon number (N) of the alkanes with the critical micelle concentration (CMC) and the thermodynamic properties of the quasi-surfactants are discussed. It can be concluded as follows: (1) The microcalorimetric method is a good method to study the process of micelle formation. (2) The CMC decreased with an increase of the carbon number (N) of the alkanes, and the relative order of the CMC of different quasi-surfactants was D2EHPA(K) > D2EHPA(Na) > D2EHPA(Li) at the same carbon number. (3) The aggregation numbers (n) and formation constant of micelle (K) increased with an increase of the carbon number (N) of the alkanes. The relative order of different quasi-surfactants was D2EHPA(K) > D2EHPA(Na) > D2EHPA(Li) at the same carbon number. (4) The Delta(r)H(m)(0) and Delta(r)S(m)(0) increased, while Delta(r)G(m)(0) decreased with an increase of the carbon number (N) of the alkanes. The relative order of the different quasi-surfactants was D2EHPA(Li) > D2EHPA(Na) > D2EHPA(K) at the same carbon number.