The electrochemical behaviour of dimethylamine borane and borohydride on platinum electrodes was investigated by cyclic voltammetry and polarization curves in discharges processes. Several overlapping peaks appear in the domain of hydrogen oxidation, i.e., in the potential range of - 1.25 V to -0.50 V versus Ag/AgCl, mainly with the borohydride. This behaviour is associated with the hydrolysis of BH4-or (CH3)(2)NHBH3. As a consequence of secondary reactions the borohydride and dimethylamine borane oxidation in 3 M NaOH solution shows, respectively, a four- to six-electron process and a four- to five-electron process in direct fuel cells. The direct oxidation of the borohydride exhibits a peak at about -0.07 V versus Ag/AgCl, while the dimethylamine borane peak is at about -0.03 V versus Ag/AgCl. For the 0.04 M concentration the borohydride displays a power density of 31 W m(-2) which is 16% higher than that of the dimethylamine borane. (C) 2007 Elsevier B.V. All rights reserved.