Compared to those from other sources, polysaccharides from medical molds with unique structural features have long been reported for a wide range of bioactivities. However, their structure-activity relationships have not been systematically summarized. This review focuses on both exopolysaccharides (EPS) and mycelia polysaccharides (MPS) from different sources of medicinal molds. The culture conditions, structural characteristics and bioactivities are reviewed. Some crucial genes involved in microbial polysaccharides synthesis are highlighted. Their food and pharmaceutical applications are also discussed. Medicinal mold polysaccharides are mainly sourced from molds in the orders of Penicillum spp., Paecilomyces spp., Aspergillus spp., Rhizopus spp., Trichoderma spp. And others. Different structural features, including glucans, mannans, chitosan, galactomannan, mannoglucan, etc. are all reported. Immunomodulatory and anti-tumor/anticancer activities are the most prominent biological activities of mold polysaccharides, which are claimed to be associated with the presence of 5-Gal f and T-Gal f in their molecules. Overall, this review helps to extend the application potential for mold polysaccharides in both food and pharmaceutical areas. [Display omitted] • Mold polysaccharides from different sources demonstrate various structural features. • The presence of Gal f is closely associated with immunomodulatory activities. • The applications of mold polysaccharides are reviewed. • Some related patterns of molds polysaccharides are summarized. [ABSTRACT FROM AUTHOR]