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The chemical composition, macromolecular characteristics, and structure of four types of <i>Tremella fuciform</i> polysaccharides (TPS) were analyzed, including one TPS that was extracted in the laboratory (L-TPS) and three commercial TPS. The effects of pH on the properties of TPS emulsions were investigated by analyzing their zeta potential, particle size, apparent viscosity, and stability. The results showed that L-TPS presented a higher percentage content of protein (2.33%) than commercial TPS (0.73–0.87%), and a lower molecular mass (17.54 × 10⁶ g/mol). Thus, L-TPS exhibited the best emulsifying activity but gave poor emulsion stability. The droplet sizes and apparent viscosity of commercial TPS-stabilized emulsions were larger or higher in acidic environments. At pH 2, the apparent viscosity was the lowest for L-TPS. Commercial TPS emulsions were most stable at pH 6, while the L-TPS-stabilized emulsion was most stable at pH 2. The obtained results revealed that the emulsifying properties of TPS varied and the effects of pH on emulsion characteristics differed, as determined from the molecular mass, macromolecular characteristics, and structure. This research is useful for expanding the application of TPS as a novel food ingredient in emulsions.