MCM‐41‐SO3H, an ordered mesoporous silica material in which MCM‐41 with covalently anchored sulfonic acid groups was used as an acidic catalyst for the rapid and ‘green’ synthesis of pyrano[3,2‐c]pyridinederivatives under solvent‐free conditions. Reusability of the catalyst, high yields, short reaction times, simplicity and easy workup are advantages of this novel synthetic procedure compared to the