The invention relates to a composite surfactant composition as well as a preparation method thereof, and mainly solves the problems that an existing surfactant is poor in oil driving efficiency during three times of oil extraction processes, meanwhile, an oil driving system contains inorganic alkaline, hurts the ground layer and an oil well, and corrodes equipment and pipelines, and demulsification is difficult. According to the composition and the preparation method, the surfactant composition comprises a cation surfactant and an anion-non-ion surfactant, wherein the cation surfactant is selected from any one of quaternary ammonium salt and quaternary amine alkali, the anion-non-ion surfactant is a surfactant containing ethoxy nonionic groups and carboxyl or sulfo anionic groups, and the mole ratio of the cation surfactant to the anion-non-ion surfactant is (1:0.01)-(1:100); by using the composition and the preparation method, the problems are solved well, and the composite surfactant composition as well as the preparation method thereof can be used in the process of three times of oil extraction in an oil field.