The Cambrian-Ordovician Mount Windsor volcanic belt in northern Australia is host to stratiform lenses of massive ferruginous chert that are spatially associated with volcanogenic massive sulfide occurrences, in particular the Thalanga zinc-lead-copper-silver deposit. The rocks are composed principally of Fe2O3 and SiO2, with very low concentrations of alkalic elements, and lithogenous elements such as Al, Zr, and Ti; they are interpreted as nearly pure chemical sediments. Textural evidence is documented of the integral role of filamentous bacteria (and/or fungi) in depositing iron from hydrothermal fluids, and of the inorganic precipitation of silica-iron-oxyhydroxide gels that subsequently matured to subcrystalline and crystalline silica forms. At least three distinct iron-accumulating microbial forms are distinguished: networks of septate filaments, nonseptate filament networks, and extremely coarse branching filaments that do not reconnect. Values for δ34S in disseminated pyrite are up to 50‰ lighter than those of contemporaneous Cambrian seawater, suggesting postdepositional colonization of some ironstones by sulfur-reducing bacteria. The site not only preserves the textural interplay of biological and inorganic depositional processes in exhalites, but also extends the oldest known instance of microbial mediation in vent-proximal hydrothermal iron precipitation to at least 500 Ma.