Anodization in HO(CH 2 CH 2 O) n H (1a, n‫;2؍‬ 1b, n‫;3؍‬ 1c, n‫)4؍‬ as an initial derivatization tool for preparing glassy carbon (GC) electrodes covalently modified with amino compounds was explored. As an amino compound to be immobilized, 4-amino-2,2,6,6-tetramethylpiperidinyl-1-oxyl (4-amino-TEMPO) was selected. When GC electrodes anodized at 2.0 V vs. Ag wire coated with AgCl in 1 containing RCH 2 CH 2 SO 3 Na (2a, R‫؍‬H; 2b, R‫؍‬OH) were treated with a N,N-dimethylformamide (DMF) or CH 2 Cl 2 solution of 4-amino-TEMPO and 1,3-dicyclohexylcarbodiimide (DCC), TEMPO-modified GC electrodes were afforded. Coverage (G G TEMPO ) of the electrode surfaces by TEMPO was estimated by cyclic voltammetry in CH 3 CN containing NaClO 4 . A TEMPO-modified GC electrode with the best G G TEMPO (1.36؋10 ؊10 mol/cm 2 ) was obtained by anodization in 1b containing 2a at the expense of 3.0 C followed by amidization in DMF for 7 d. On cyclic voltammetry, the TEMPO-modified GC electrode showed good and stable electrocatalytic ability for oxidation of allyl alcohol in the presence of 2,6-lutidine.