Solvent-free esterifications, polyesterification and selective esterification of various carboxylic acids and alcohols catalyzed by functional surfactant are researched systemically in the paper. On the basis of esterification of oleic acid and 1-octanol effectived catalyzed by dodecylbenzene sulfonic acid (DBSA), we synthesize various Lewis acid functional surfactant (LAFS) from AlCl3 CuCl2, SnCl4, ZnCl2, MgCl2, CoCl2 and soldium dodecylbenzene sulfonate, soldium dodecyl sulfate, soldium dodecyl sulfonate by decomposition reaction。And used oleic acid and 1-ocanol as typical reaction substrates, their activation of catalyzing esterification are investigated on the condition of free solvent and at room temperature. By comparison of esterification catalyzed by sulfuric acid, toluence sulfuric acid, bluestone, copper toluence sulfate, sodium dodecylbenzene sulfonate, we research FS catalyzed esterification mechanism of removing water, and the micelle mechanism is confirmed furtherly by TEM. For investigating applicability and application scope of these FS catalysts to esterification, we use the screened effective catalysts to catalyze esterification of linear and nonlinear carboxylic acids and alcohols, substrates with functional group, polysesterification of dicarboxylic acid and diol, selective esterification. This study indicates that the catalysts FS with both catalysis function and surfactant function play dual roles during the esterification. First, as Brosted and Lewis acids, they effectively catalyze the esterification reaction. Secondly, as surfactants, they can form reverse micelles in system to separate water produced from the product ester and promotes the reaction equilibrium towards the product. The esterification method has following green chemistry advantages: Firstly, there is no need for any solvent, even water. Secondly, the method no need to remove water produced to promote the equilibrium process to shift towards the product side, saving energy. Thirdly, the condition of reaction is mild, even esterification can carry out smoothly at room temperature. And fourthly, hydrophobicity of FS enhances contact of catalyst and reactants, and quiken velocity of reaction. In conclusion, esterifications catalyzed by functional surfactant are a relative green chemistry method.