Glucose is the most abundant monosaccharide as it is the primary unit of cellulose and starch, which are the more relevant feedstocks for biorefineries. Dehydration of glucose can lead to anhydroglucoses, whose interest has been increasing due to its potential industrial use. Commercial sulfonic polymer resins and a synthesized organic–inorganic mesoporous material were taken as Brønsted acid catalysts. High hexose conversion (up to 98%) and selectivity to anhydroglucoses (~80%) could be reached, turning this process into an alternative route to carbohydrate pyrolysis that presents an energy-intensive downstream. Hexose conversion to anhydroglucoses was related to the amount of acid sites, and the removal of one molecule of water from hexoses to produce anhydroglucoses was found as the preferential dehydration route over a bare Brønsted acid catalyst in anhydrous polar aprotic solvent (DMF) at mild conditions. Product distribution changed dramatically upon catalyst deactivation with HMF and fructose emerging as relevant products. It was suggested that an additional Lewis surface is produced during the deactivation process, probably arising from the formation of insoluble high molecular weight compounds in acidic media.