Intense weathering of copper orebodies in New South Wales and Queensland, Australia has produced an unusual suite of secondary copper minerals comprising chrysocolla, azurite, malachite and the phosphates libethenite and pseudomalachite. The phosphates persist in outcrop and show a marked zoning with libethenite confined to near-surface areas. Abundant chrysocolla is also found in these environments, but never replaces the two secondary phosphates or azurite. This leads to unusual assemblages of secondary copper minerals, that can, however, be explained by equilibrium models. Data from the literature are used to develop a comprehensive geochemical model that describes for the first time the origin and geochemical setting of this style of economically important mineralization.