Abstract-Coesite and stishovite are developed in shock veins within metaquartzites beyond a radius of~30 km from the center of the 2.02 Ga Vredefort impact structure. This work focuses on deploying analytical field emission scanning electron microscopy, electron backscattered diffraction, and Raman spectrometry to better understand the temporal and spatial relations of these silica polymorphs. a-Quartz in the host metaquartzites, away from shock veins, exhibits planar features, Brazil twins, and decorated planar deformation features, indicating a primary (bulk) shock loading of >5 < 35 GPa. Within the shock veins, coesite forms anhedral grains, ranging in size from 0.5 to 4 lm, with an average of 1.25 lm. It occurs in clasts, where it displays a distinct jigsaw texture, indicative of partial reversion to a less dense SiO 2 phase, now represented by microcrystalline quartz. It is also developed in the matrix of the shock veins, where it is typically of smaller size (<1 lm). Stishovite occurs as euhedral acicular crystals, typically <0.5 lm wide and up to 15 lm in length, associated with clast-matrix or shock vein margin-matrix interfaces. In this context, the needles occur as radiating or subparallel clusters, which grow into/over both coesite and what is now microcrystalline quartz. Stishovite also occurs as more blebby, subhedral to anhedral grains in the vein matrix (typically <1 lm). We propose a model for the evolution of the veins (1) precursory frictional melting in a microfault (~1 mm wide) generates a molten matrix containing quartz clasts. This is followed by (2) arrival of the main shock front, which shocks to 35 GPa. This generates coesite in the clasts and in the matrix. (3) On initial shock release, the coesite partly reverts to a less dense SiO 2 phase, which is now represented by microcrystalline quartz. (4) With continued release, stishovite forms euhedral needle clusters at solid-liquid interfaces and as anhedral crystals in the matrix. (5) With decreasing pressure-temperature, the matrix completes crystallization to yield a microcrystalline quasi-igneous texture comprising quartz-coesite-stishovite-kyanite-biotitealkali feldspar and accessory phases. It is possible that the shock vein represents the locus of a thermal spike within the bulk shock, in which case there is no requirement for additional pressure (i.e., the bulk shock was ≃35 GPa). However, if that pressure was not realized from the main shock, then supplementary pressure excursions within the vein would have been required. These could have taken the form of localized reverberations from wave trapping, or implosion processes, including pore collapse, phase change-initiated volume reduction, and melt cavitation.