The electrochemical oxidation of borohydride was investigated by using various ad-atom modified Au(111) electrodes in alkaline media in comparison to Au(111) single crystal, polycrystalline Au, Pt and Zn electrodes. The catalytic activity of gold towards borohydride oxidation has tended to increase in more alkaline media as reflected in the oxidation peak in the concentration range of NaOH (0.01–2.0 M) studied. Additional shift on the oxidation peak potential of borohydride on Pt and Zn ad-atom modified Au(111) electrodes was observed for both ad-atom modified electrodes to more negative potentials compared to that of bare electrodes, respectively. The ad-atom modified Au(111) electrodes surfaces do not only provide a superior electrical contact, but also accelerates electron transfer as proven by the increase in peak current and positive shift in the peak potential.