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Licorice is known as "Gan-Cao" in traditional Chinese Medicine (TCM), belonging to the genus Glycyrrhiza (Family: Fabaceae/Leguminosae). It has a long medicinal history and wide applications in China. Polysaccharides of licorice (LPs) are one of the key bioactive components. As herbal polysaccharides attracted increasing interest in the past several decades, their extraction, isolation, structural characterization, pharmacological activities, and medicinal application have been explored extensively. It is worth heeding that the method of extraction and purification effects LPs, apart from specie and origin specificity. This review evaluates the method of extraction and purification and demonstrates its performance in gaining specific composition and its structure-activity relationship, which might lead the readers to a fresh horizon for developing advanced treatment strategies. It is recently reported that the conformation of LPs plays a vital role as biopolymers, such as selenized modification, microencapsulation, nanocomposite, liposome formulation, drug/hydrogel combinations, biosensor device, and synergistic effect with a vaccine. In addition, LPs showed a good thermodynamics profile, as these properties enable them to interact with additional supramolecular interaction by chemical modifications or copolymerization. Functional polymers that are responsive to various external stimuli, such as physical, chemical, and biological signals, are a promising study topic. Thus, LPs are emerging as a new biomaterial that can enhance intended formulation along exerting its inherent medicinal effects. It is hoped that this review will provide a basis for the utilization and further developments of licorice polysaccharides in the vast medium. [ABSTRACT FROM AUTHOR]