As an important forestry biomass resource, rosin has a wide range of applications in medicine, adhesives, surfactants and other fields. Using natural dehydroabietic acid as a raw material, dehydroabietic acid-based phosphorus monoester (DPM) and diester (DPD) surfactants were designed and synthesized. The chemical structures and self-assembly properties were characterized by FT-IR, NMR and TEM, and the effects of pH on critical micelle concentration, γCMC, emulsifying properties, foam properties and micelle morphology were studied. The results showed that the CMC, γCMC value and aggregate morphology had certain pH responsiveness. The γCMC value under acidic conditions was smaller than γCMC under alkaline conditions, and the foaming performance and foam stability under acidic conditions were better than those under alkaline conditions. TEM micelle morphology studies have shown that DPM and DPD surfactants can self-assemble into rod-shaped and spherical micelle morphologies with a pH change in an aqueous solution. At the same pH, the foaming and emulsification properties of DPD were better than those of DPM. The best foaming and emulsification ability of DPD were 11.8 mL and 175 s, respectively. At the same time, the foaming ability of DPD is also affected by pH. DPD has excellent foaming properties in acidic conditions, but these disappeared in neutral conditions.