The Ediacaran–Cambrian transition was one of the most critical intervals in Earth history. During this interval, widespread chert was precipitated, commonly as a stratal wedge in carbonates, along the southern margin of the Yangtze Platform, South China. The chert wedge passes into a full chert succession further basinward to the south-east. Four lithotypes of chert are identified across the marginal zone in western Hunan: mounded, vein, brecciated and bedded chert. The mounded chert is characterized by irregular to digitiform internal fabrics, generally with abundant original vesicles and/or channels that mostly are lined by botryoidal chalcedony cements with minor quartz and barite crystals. The host chert (or matrix) of these mounds is dominated by amorphous cryptocrystalline silica, commonly disseminated with pyrite. The vein chert, with minor quartz locally, generally cross-cuts the overlying dolostone and chert horizons and terminates under the mounded and/or bedded chert bodies. The brecciated chert commonly occurs as splayed ‘intrusions’ or funnel-shaped wedges and cross-cuts the topmost dolostones. The bedded chert, the most common type, generally is thin to medium-bedded and laminated locally; it is composed of amorphous silica with minor amounts of black lumps. Microthermometry of fluid inclusions from vein and void-lining minerals (mainly quartz and barite) revealed homogenization temperatures from 120 to 180°C for the trapped primary fluids. Compositionally, these chert deposits generally are pure, with SiO2 > 92 wt%, and only minor Fe2O3 and Al2O3 contents, most of which show positive Europium anomalies in rare earth element patterns, especially for the mounded chert. All these data suggest that the marginal zone chert deposits resulted from a low-temperature, silica-rich hydrothermal system, in which the mounded chert was precipitated around the releasing vents, i.e. as silica chimneys. The vein and splayed brecciated chert, however, was formed along the syndepositional fault/fracture conduits that linked downward, while the bedded chert was precipitated in the quieter water column from the fallout of hydrothermal plumes onto the sea floor. These petrological and geochemical data provide compelling evidence and a new clue to the understanding of the extensive silica precipitation; rapid tectono-depositional and oceanic changes during the Ediacaran–Cambrian transition in South China.