Hierarchical porous gold films with a well-defined bimodal architecture have been made by electrodepositing gold at a constant current around a close-packed assembly of raspberry-like latex spheres (1200/60nm) followed by template removal. Electrodeposition was stopped when the gold was either ½ layer or 1½ layer thick as evident from oscillations in the potential vs time traces. Scanning electron microscopy (SEM) images show the hierarchical pore structure with an ensemble of small ∼20nm openings located in a large ∼1200nm diameter macropore. Prior to electrochemical characterization, the electrodes were cleaned either chemically and/or via UV radiation and X-ray photoelectron spectroscopy (XPS) was used to evaluate the presence of residual polystyrene. Of the three cleaning methods investigated, sonication in chloroform–acetone followed by UV radiation proved best. The surface area of the hierarchical porous gold electrodes, determined by integrating the area under the gold oxide peak, was 4× larger than a bare gold electrode and 2× larger than a macroporous gold electrode prepared using unimodal, 1200nm diameter latex spheres as the template. The electrochemical performance of the electrodes relative to the macroporous gold and flat gold was undertaken using cyclic voltammetry. The results show that the non-Faradaic current scales linearly with electrode area while the Faradaic current of a diffusing electrochemically reversible redox probe (ferrocene methanol) does not. For an adsorbed redox couple (ferrocene hexanethiol), the voltammetric wave shapes and surface coverage were different for the different electrodes.