The Catalán Flow in the southernmost Paraná Volcanic Province exhibits two extensive red and gray to white tiers and an areally vast breccia stockwork, both of which are unique within intraplate large igneous provinces. To comprehend the processes responsible for the formation of these structures, we integrated the study of satellite images with field surveys and the interpretation of published geochemical analyses. During the Early Cretaceous, a 30-m-thick layer of quartz andesite known as the Catalán Flow covered the 160-m-thick Botucatu + Guará formations, which had transformed into the Guarani Paleoaquifer. This flow consists of a lower Tier 1, which appears gray in satellite images and medium gray to white in the field, and an upper Tier 2, which is red in both images and in the field. Amethyst and agate geodes are present in Tier 1 but are absent in Tier 2. Within an area exceeding 100 by 100 km, a breccia stockwork composed of quartz andesite fragments can be found. These fragments either include silicified sandstone or hydrothermal zeolites. The chemical composition of rocks from Tier 2 features a loss on ignition (LOI) of less than 1.5 wt% and a composition similar to the original lava. In contrast, Tier 1 underwent significant alteration, particularly a reduction in SiO2 and K2O, along with an increase in Fe2O3T, with LOI exceeding 1.5 wt% and reaching up to 8 wt%. The formation of hematite and the reddening of the rock in Tier 1 were a result of heated, oxidizing aquifer water percolating through the lava. Subsequently, reducing, aquifer hot water percolated, causing intense chemical and mineralogical alteration in the previously oxidized flow, resulting in a gray to white color and the formation of amethyst and agate deposits. Tier 1 represents the reduced lower layer of the flow, while Tier 2 is the remaining red upper portion. Comparative fluid activity is observed in red and white dunes in the Etendeka, as well as in basalts from various environments. The breccia stockwork was formed through explosive hydrothermal processes beneath the upper crust, where overpressured fluids came into direct contact with the atmosphere, leading to flash vaporization. The structures observed are the outcome of the distant influence of paleodune patterns on the Catalán Flow, which corresponds to the presence of higher dunes in the two tiers and sand sheets in the breccia stockwork. The processes responsible for the two-tier (oxidation and reduction) and breccia formation (explosive pressure release and sand injection near the surface) are recognized in various hydrothermal systems worldwide. However, the extensive areal coverage and homogeneity of these features, coupled with the presence of world-class amethyst deposits, make the Paraná Volcanic Province unique among large igneous provinces worldwide.