This study conducted counter-current solvent extraction to investigate the influence of solvent/solution volumetric ratio, solvent flow rate, and surfactant concentration on extraction efficiency. Fitting formulas for predicting the partition coefficients of the contaminant and surfactant between the aqueous and solvent phases were developed to optimize the counter-current solvent extraction. It is found that the solvent/solution volumetric ratio and the surfactant concentration had greater impact than the solvent flow rate on the extraction efficiency. The relationship between the partition coefficient K and the solvent/solution volumetric ratio or surfactant concentration was closely related to power function. Besides, the accuracy of the fitting formulas was consistent with the experimental results.