Gold nanoparticles (AuNPs) were deposited onto glassy carbon (GC) by constant potential electrolysis (CPE) using various sets of potential and duration from -0.3 to 0.7 V/SHE and 10 to 1800s, respectively. The physico-chemical characteristics of the as-obtained deposits were investigated by cyclic voltammetry (CV) in H2SO4, field emission gun scanning electron microscopy (FEG-SEM), and Pb underpotential deposition (UPD). Their performances toward the oxygen reduction reaction (ORR) in a NaCl-NaHCO3 (0.15 M/0.028 M, pH 7.4) neutral solution were examined and correlated to AuNPs size and density. The best results were obtained using the deposits which exhibited a high density (555 +/- 49 mu m(-2)) of relatively small AuNPs (25 +/- 12 nm). The Koutecky-Levich treatment was systematically applied to all the deposits in order to determine the number of electrons n exchanged for the ORR in the potential range from 0.1 to -1.0 V/SHE. The values of the cathodic transfer coefficients beta n were also extracted and compared to the values reported for unmodified GC and bulk Au. A map of the beta n values as a function of AuNPs electrodeposition potential and duration was also provided. (C) 2013 Elsevier Ltd. All rights reserved.