The present invention provides a novel anhydrous composition of small-molecule polysaccharides, consisting of at least a small-molecule polysaccharide and an anhydrous base. The formulation of the anhydrous composition of small-molecule polysaccharides allows the small-molecule polysaccharide to maintain a molecular size of 12-22 nm and the direct penetration of the small-molecule polysaccharide across the horny layer of skin. The present invention also provides a method of effectively maintaining skin hydration level in a subject in need thereof, comprising topically administering to the subject an anhydrous composition of small-molecule polysaccharides.