Polysaccharides obtained from Gynostemma pentaphyllum (Thunb.) Makino have promising prospects in functional food and nutraceuticals due to its broad range of biological activities including antioxidant, immunomodulatory, antitumor, hepatoprotective, neuroprotective, and antifatigue activities. These beneficial biological activities are related to chemical composition and structure of the G. pentaphyllum polysaccharides. The molecular weight, monosaccharide composition, and chemical structures could be influenced by both different extraction/purification techniques employed to obtain polysaccharide enriched products. The purpose of this article is to review previous and current literature regarding the extraction, purification, structural characterization, and biological activity of G. pentaphyllum polysaccharides. This review provides a useful bibliography for the further investigation, production, and application of G. pentaphyllum polysaccharides as functional foods and nutraceuticals.