The ammonia borane (NH3BH3) oxidation reaction (ABOR) was studied on gold electrodes using the rotating disk electrode (RDE) setup and coupled physical techniques: on-line differential electrochemical mass spectrometry (DEMS) and in situ Fourier transform infrared spectroscopy (FTIR). Non-negligible heterogeneous hydrolysis in the low-potential region was asserted via molecular H-2 detection. As a consequence, the number of electron exchanged per BH3OH- species is ca. 3 at low potential, and only reaches ca. 6 above 0.6 V vs. RHE. These figures were confirmed by Levich and Koutecki-Levich calculations using the RDE experiments data. The nature of the ABOR intermediates and products was determined using in situ FTIR. While BH2 species were detected during the ABOR, it seems that its adsorption onto the Au electrode proceeds via the O atom, in opposition to what happens during the borohydride oxidation reaction (BOR). Therefore, it is likely that the mechanism of the ABOR differs from that of the BOR. From the whole set of data (RDE, DEMS, FTIR), a relevant reaction pathway was proposed, including competition between the BH3OH- heterogeneous hydrolysis and oxidation at low potential, and preponderant oxidation at higher potential. Finally, a simplified kinetic modeling accounting with this reaction pathway was proposed, which nicely fits the stationary (i vs. E) ABOR plot. (C) 2012 Elsevier Ltd. All rights reserved.