The electrochemical deposition and reoxidation of Au on the basal plane of highly oriented pyrolytic graphite (HOPG) immersed in a 5 mM AuCl4-/6 M LiCl solution is reported. Scanning electron microscopy (SEM) and ex-situ atomic force microscopy (AFM) demonstrate that An nanoparticles, similar to3.3 nm in height and similar to10 nm in diameter, are deposited at times less than similar to1 s. The density of nanoparticles, 6 x 10(9) cm(-2), is of the same order of magnitude as the surface point defect density, suggesting that point defects act as nucleation sites for An electrodeposition. A small subset of the Au nanoparticles (similar to7%) continues to grow between 1 and 50 s, reaching a height of similar to150 nm and a diameter of similar to300 nm. At times greater than 50 s, the larger particles coalesce to yield a surface comprised of a low density (similar to2 x 10(6) cm(-2)) of micrometer-size An crystallites surrounded by An nanoparticles. Double potential step chronocoulometric experiments demonstrate that the electrodeposition of Au is chemically irreversible, a finding supported by SEM and AFM observations of An nanoparticles and larger crystallites on the surface after long periods of reoxidation (>3600 s). Au nanoparticles are observed to be preferentially deposited on the upper plane of step edges, a consequence of the nonuniform surface electron density that results from relaxation of the graphite lattice near steps.