Three-dimension (3D) belt-like polyaniline (PAN) network has been prepared via electrochemical polymerization of aniline on p-phenylenediamine (PDA) functionalized glassy carbon electrode (GCE) using a three-step electrochemical deposition procedure. PDA was covalently binded on GCE via the formation of carbon-nitrogen bond between amine cation radical and the aromatic moiety of CCE surface using electrochemical oxidation procedure. X-ray photo-electron spectroscopy (XPS) and cyclic voltammetry have been performed to characterize the attachment of PDA on CCE. The images or scanning electron microscope (SEM) show that the 3D belt-like PAN network is uniform. The width and thickness of the PAN belt varies in the range of 1.5-5.5 mu m and 0.1-0.8 mu m, respectively. The distance between the belt-contacts ranges from 2.5 to 15 mu m. The 3D belt-like PAN network modified GCE (PAN-PDA/GCE) exhibits an improved electro-activity of PAN at an extended pH up to 7.0. The PAN-PDA/GCE not only immobilizes but also leads to a direct electrochemical behavior of cytochrome c (Cyt c). The immobilized Cyt c maintains its activity, showing a surface-controlled electrode process with the electron-transfer rate constant (k(s)) of 14.8 s(-1) and electron-transfer coefficient (alpha) of 0.48, and could be used for the electrocatalytic reduction of hydrogen peroxide (H2O2). (C) 2009 Elsevier Ltd. All rights reserved.