The 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 (1) 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. (C) 2015 Elsevier Ltd. All rights reserved.