Polysaccharide is the most abundant natural polymer in nature. The molecular chains of polysaccharides are usually substituted by hydrophobic side groups, giving them a natural amphiphilicity. Therefore, it can be well adsorbed onto the multiphase interface, having the ability to improve the compatibility between solid-liquid and liquid-liquid phases. In addition, the unique physicochemical structure enables polysaccharides to have good rheological properties in water and have the ability to form gel networks, which can exhibit good interfacial adsorption ability under low surface activity, so they are often used for emulsifying, dispersing, thickening and stabilizing multiphase systems. The balancing of the hydrophilic-hydrophobic level of polysaccharides was obtained by appropriate chemical modifications, which also give them special surface properties making an excellent green macromolecular surfactant. Based on this, the article mainly introduces the application of naturally abundant polysaccharides in surfactants, mainly including cellulose, starch, hemicellulose, chitin, natural gum, etc. The effects of chemical structures and modifications of polysaccharides on their emulsifying, dispersing, demulsifying, solubilizing properties were analyzed; the research progress and application potential of polysaccharides and their derivatives in surfactants were described.