A simple one-step procedure is introduced for the preparation of diazonium-enzyme adducts. The direct electricallyaddressable deposition of diazonium-modified enzymes is examined for electrochemical sensor applications. Thedeposition of diazonium-horseradish peroxidase leads to the direct electron transfer between the enzyme and electrodeexhibiting a heterogeneous rate constant,
ks, of 10.3 ± 0.7 s
-1 and a
Ep of 8 mV (
v = 150 mV/s). The large
ks andlow
Ep are attributed to the intimate contact between enzyme and electrode attached by one to three phenyl molecules.Such an electrode shows high nonmediated catalytic activity toward H
2O
2 reduction. Future generations of arrayedelectrochemical sensors and studies of direct electron transfer of enzymes can benefit from protein electrodes preparedby this method.