AbstractSurfactants made from modified lignin are attracting growing attention; therefore, a lignin-phenol nonionic surfactant named ML-AL has been prepared by modifying liquefied industrial alkali lignin (L-AL). Its basic physical and chemical properties have been shown to be favorable. In this work, anionic surfactants of sodium fatty acid soap (carbon numbers 12, 16, and 18) and sulfur-containing anionic surfactants (sodium dodecyl sulfate and sodium dodecyl benzene sulfonate) were chosen to mix with ML-AL in water-soluble media. The surface properties of each binary mixed solution system with anionic surfactant were investigated. At the same time, the mixed micelles formed by ML-AL and each anionic surfactant were studied. Non-ideal mixed micelles were obtained via ML-AL and the tested anionic surfactant. The interaction parameter (βM) and excess free energy (ΔGexcess) were both negative. Meanwhile, the critical micelle concentration (CMC) values of mixed systems (formed by ML-AL and each anionic surfactant in aqueous solution) were lower than those of a single-component system (ML-AL or single anionic surfactant). There was an optimum dosage ratio of about 0.4 in terms of synergistic effects. This research could provide a foundation for practical applications of combinations with anionic surfactants in aqueous solution.