AbstractBackgroundSupramolecular technology has been widely applied in cosmetics due to its ability to enhance the stability of active substances and reduce their irritation potential. The synergistic interaction between polysaccharides can produce new products with characteristics and rheological properties that make them suitable for various applications.ObjectiveThe supramolecularly assembly of Dendrobium officinale polysaccharide (DOP) and hyaluronic acid (HA) was produced, and its moisturizing effect was verified to provide a basis for the application of supramolecular technology in cosmetic functional raw materials.MethodsThe supramolecular structure of polysaccharide assembly samples was verified through scanning electron microscopic observation. Moisture absorption and the ability of samples to resist cell drying damage before and after supramolecular assembly were evaluated by moisture absorption experiments and a cell drying damage model, respectively. Furthermore, this study validated the moisturizing effect of the supramolecular compositions during their application in cosmetics through tests of skin moisture content in extremely dry environments (during the winter season of Beijing, China), skin roughness and scale index, and trans epidermal water loss.ResultsThe supramolecular composition appeared as a large sheet‐like structure under a scanning electron microscope. Further, the supramolecular composition had significantly improved moisture absorption performance and could effectively resist cell drying damage. In an extremely dry environment, the composition showed excellent moisturizing performance and effectively improved skin scale and roughness.ConclusionsThe supramolecular assembly of DOP and HA has a synergistic moisturizing effect; thus, it can be expected to have a good moisturizing effect when applied to cosmetics.