This investigation describes the surface characterization of rabbit immunoglobulin G (IgG) conjugated with gold nanoparticles. Goat anti-rabbit immunoglobulin G tagged with 5nm gold nanoparticles was applied to detect the IgG. Then, the autocatalyzed deposition of Au 3+ onto the surface of anti-IgGAu increased the surface area per gold nanoparticle. The immobilization chemistries and the atomic concentrations of Au 4f , P 2p , S 2p , C 1s , N 1s and O 1s of the resulting antibody-modified Au electrodes were determined by X-ray photoelectron spectroscopy (XPS). The sulfur that is involved in the cysteamine binding and the enlargement of the gold nanoparticles are identified using cyclic voltammetry. The results reveal that the surface area per gold particle, following the autocatalyzed deposition Au 3+ on the surface of anti-IgGAu, was approximately seven times higher than that before deposition.