The surface properties of gold-associated pyrite play a determining role in pyrite dissolution in gold extraction. However, the surface properties of pyrite have been always studied without the consideration of gold coupling. In this study, the reactivity, surface speciation and topography of pyrite after its oxidation with and without gold coupling in the presence of Fe3+, a strong oxidant widely used in the industry, were studied and compared using EIS (Electrochemical Impedance Spectroscopy), Cryo-XPS (X-ray Photoelectron Spectroscopy at-145 degrees C) and AFM (Atomic Force Microscopy), respectively. It was interesting to find that gold could catalyse Fe3+ reduction and gold coupling significantly enhanced pyrite oxidation with more oxidised iron species such as Fe3O4/Fe2O3 and FeOOH and oxidised sulphur species such as Sn2-/S-8 and SO32- formed on the pyrite surface. Gold coupling also resulted in a much rougher and larger surface area of pyrite, appreciably increasing the electrochemical reactivity of pyrite for its successive oxidation and dissolution. These findings provide insights into the physicochemical properties of gold-associated pyrite, which can be exploited to improve the gold extraction process.