Anhydrofructose (AF) pathway describes the catabolism of alpha-1,4-glucans of glycogen, starch and maltosaccharides to various metabolites via the central intermediate AF. The reaction sequence of the pathway consists of more than 10 enzymatic steps. This pathway occurs in certain bacteria, fungi, algae and mammals. In this communication, the AF pathway and its regulatory mechanisms in these organisms are presented and the metabolites of this pathway as antioxidants and antimicrobials in biotic and abiotic stress responses and in carbon starvation signaling are discussed.