3-Aminophenylcalix[4]pyrrole (3APCP) was grafted to a glassy carbon (GC) surface during the electrochemical oxidation process in 0.1 M tetrabutylammoniumtetra-fluoroborate (TBATFB) containing acetonitrile solution. The presence of a surface film was confirmed electrochemically by comparing voltammograms of dopamine and ferricyanide redox probes at the bare and modified electrodes. Reflection-absorption infrared spectroscopy (RAIRS), XPS, atomic force microscopy (AFM), ellipsometry and the contact angle measurements were also employed to characterize 3APCP film on GC electrode. RAIRS analysis revealed that calix[4]pyrrole was bonded to the glassy carbon surface via the etheric linkage. The stability of the modified GC electrode was also studied. Copyright © 2011 John Wiley & Sons, Ltd.