Patterns in white mica (muscovite, paragonite, and phengite) Al-Si chemistry (Tschermak substitution) were examined for the Archean Kanowna Belle and Sunrise Dam gold deposits in the Eastern Goldfields of Western Australia, using short-wave infrared (SWIR) spectrometry of drill core samples. Both of these deposits represent greenschist-facies, structurally controlled, >10-Moz gold systems with broadly similar host rocks and superimposed metasomatic hydrothermal alteration halos that extend for up to 3 km from the economic zone. However, zonation toward gold mineralization at Kanowna Belle is associated with increasingly longer wavelength white mica, whereas Sunrise Dam comprises the opposite pattern. The study also found that gold mineralization at Kanowna Belle is associated with quartz, chalcopyrite, and pyrite with negative δ34S values and a relative lack of carbonate, chlorite, and paragonite (Na-rich white mica), whereas gold mineralization at Sunrise Dam is associated with paragonite as well as carbonate, Fe-rich chlorite and pyrite with positive δ34S values and a relative lack of quartz and chalcopyrite. Thermodynamic numerical modeling revealed that these contrasting patterns in white mica Tschermak substitution (and associated alteration mineralogy) can be explained by two different types of ore fluids, namely (1) oxidized, alkaline, and silica-rich at Kanowna Belle; and (2) reduced, acid, Fe-rich and silica-poor at Sunrise Dam, though the sources of these contrasting fluids are less clear. Importantly for explorers, spectral measurement (using drill core, field, airborne, and potentially satellite hyperspectral SWIR data) of gradients (especially within a given geologic unit) in white mica absorption wavelength (Tschermak substitution) represents a potential vectoring tool for the discovery of new Archean hydrothermal gold systems.