A "two-phase protocol" is proposed to prepare gold electrode with controlled surface and crystallographic properties. Gold nanoparticles were first electrodeposited onto a glassy carbon (GC) electrode. Next, gold particles were allowed to be deposited by a colloidal chemical seeding process onto the previously electrodeposited gold nanoparticles on the GC electrode and thus Au-over-Au electrodes were fabricated. It was found that the surface area, crystallographic orientation and the surface morphology of the prepared electrodes can be controlled by adding acid or additive (I(-)) to the seeding media. An electrode ensemble with surface area of as high as 7.5 x 10(-3) cm(2) and ca. 60% Au(1 1 1) facet was fabricated by maintaining the seeding medium at pH 2.15. The application of the prepared electrode was demonstrated briefly in the electrochemical detection of arsenic(III) in water. (C) 2009 Published by Elsevier B.V.