The chemical structures and functional properties of plant-based polysaccharides are critically influenced by extractive solvents, but their roles are not clear. In this study, the structural characteristics and multiple bioactivities of polysaccharides (VVPs) subjected to water (VVP-W), alkalis (sodium hydroxide, VVP-A), and acids (citric acid, VVP-C) as extractive solvents are investigated systematically. Of the above three polysaccharides, VVP-W exhibited the highest molecular weights, apparent viscosity, and viscoelastic properties. Functional analyses revealed that VVP-C had an excellent water-holding capacity, foaming properties, and emulsifying capacity, while VVP-A exhibited a promising oil-holding capacity. Moreover, VVP-C displayed strong inhibitory effects on α-amylase and α-glucosidase, which could be attributed to its content of total phenolics, proteins, and molecular weights. These findings have important implications for selecting the appropriate extraction techniques to obtain functional polysaccharides with targeted bioactive properties as food additives.