This review article gives a survey of the selected principal biosynthetic pathways that lead to the most important polysaccharides occurring in foods and in food raw materials and informs non-specialist readers about new scientific advances as reported in recently published papers. Subdivision of the topic is predominantly done via biosynthesis and includes reserve polysaccharides (starch and glycogen, fructans), plant cell wall polysaccharides (cellulose and callose, pectin), and animal polysaccharides (chitin and glycosaminoglycans). Extensively used are the reaction schemes, sequences, and mechanisms with the enzymes involved and detailed explanations using sound chemical principles and mechanisms.