electrocatalysis fuel cell carbohydrate sensor multi-electron EC'mechanism catalyst heterogenisation A B S T R A C TThe enzymeless and operationally simple electrocatalytic oxidation of carbohydrates by "heterogenised" 4-benzoyloxy-TEMPO either (i) immobilised as microcrystals at a glassy carbon electrode surface or (ii) embedded into a polymer of intrinsic microporosity (PIM-EA-TB with 1027 m 2 g À1 BET surface area and highly rigid framework structure) has been studied in aqueous phosphate buffer of pH 12. It is shown that in contrast to microcrystal deposits, 4-benzolyoxy-TEMPO co-immobilised within PIM-EA-TB give stable catalytic responses for both, stationary and rotating disc electrode systems and for oxidation of glucose, sorbitol, and sucrose. The rigidity and intrinsic microporosity of PIM-EA-TB allow (slow) substrate and product diffusion, whilst maintaining 4-benzoyloxy-TEMPO immobilised in active molecular form.