Abstract The oil-recovery effectiveness of a chemical flood has been proved related to the phase behavior of the brine/oil/surfactant system. In particular, it is advantageous to formulate the system so that optimal three-phase behavior is obtained. However, it also has been demonstrated that all the optimized systems are not equivalent in terms of solubilization, interfacial tensions (IFT's), and oil-recovery efficiency. This paper addresses the conditions that promote high solubilization in microemulsions, a property correlated to the values of the IFT and therefore correlated to the ability of such systems to displace the oil in porous media. When one formulation parameter is changed, another parameter must be varied at the same time for compensation to reoptimize the system. The mechanism of solubilization is investigated experimentally by considering the usual formulation parameters: salinity, oil type, alcohol type and concentration, and surfactant structure and type (anionics and nonionics). The results are interpreted in terms of interaction energies between surfactant, oil, and water. In particular, the role of the alcohol and its impact on the solubilization by amphiphilic systems are discussed in detail and interpreted. Moreover, the concepts developed in this paper explain the effect of the surfactant structure and therefore aid in the design of amphiphilic molecules exhibiting a high solubilizing power for given conditions of brine, temperature, etc.