Dimethylamine borane (DMAB) electro-oxidation in alkaline media was studied using static and rotating gold single-crystal electrodes in the hanging-meniscus configuration. DMAB oxidation showed a strong sensitivity towards surface structure on gold electrodes. In situ Fourier transform infrared (FTIR) spectroscopy revealed that the potential-dependent cleavage of the B-N bond is one of the initial steps of the oxidation process. FTIR also showed that dimethylamine is oxidised in the potential range of gold oxide formation. © 2011 Elsevier Ltd. All rights reserved.