The free radical 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl (4B-TEMPO) is active as an electrocatalyst for primary alcohol oxidations when immobilised at an electrode surface and immersed into an aqueous carbonate buffer solution. In order to improve the catalytic process, a composite film electrode is developed based on (i) carbon microparticles of 2–12 μm diameter to enhance charge transport and (ii) a polymer of intrinsic microporosity (here PIM-EA-TB with a BET surface area of 1027 m2 g−1). The latter acts as a highly rigid molecular framework for the embedded free radical catalyst with simultaneous access to aqueous phase and substrate. The resulting mechanism for the oxidation of primary alcohols is shown to switch in reaction order from first to zeroth with increasing substrate concentration consistent with a kinetically limited process with competing diffusion of charge at the polymer layer-electrode interface (here the “LEk” case in Albery-Hillman notation). Reactivity optimisation and screening for a wider range of primary alcohols in conjunction with DFT-based relative reactivity correlation reveals substrate hydrophobicity as an important factor for enhancing catalytic currents. The PIM-EA-TB host matrix is proposed to control substrate partitioning and thereby catalyst reactivity and selectivity.