Geologic samples are extremely diverse and share a tendency for both heterogeneity and complexity. This is especially true for ores, which commonly result from a complex interplay of processes in highly dynamic environments. In recent years, a number of tools allowing the chemical mapping of major (e.g., mineral liberation analysis, MLA), minor (e.g., electron microprobe, EPMA), and trace (e.g., laser ablation-inductively coupled plasma-mass spectrometry, LA-ICP-MS) elements in geologic samples at ~1-to 50-μm resolution and over mm2areas have seen rapid development and have become readily available. To date, the application of synchrotron-based X-ray fluorescence (SXRF) mapping has been limited to addressing key questions because of low availability and high cost. This paper demonstrates how recent advances in X-ray fluorescence detector technology are bringing new possibilities to ore petrology. Millisecond dwell times allow collection of thin section size maps at resolutions of a few μm in hours, while improvements in data analysis software simplify the production of quantitative elemental maps. Based on the imaging of six samples representative of different commodities (Pt, U, Cu, Ge) and different geologic contexts (PGE deposit; sandstone-hosted U deposit; vein-type polymetallic hydrothermal deposit; iron oxide-copper-gold (IOCG) deposit), we demonstrate that megapixel SXRF (MSXRF) can efficiently provide the information necessary to understand metal speciation in the context of thin section-scale textural complexity. Image analysis revealed a number of new results for the studied deposits, for example, (1) the distribution of micrometer-sized Pt-rich grains and Ti mobility during the formation of schistosity at the Fifield Point prospect (New South Wales, Australia); (2) the presence of Ge contained in organic matter and of Hg minerals associated within quartzite clasts in the Lake Frome U ores (South Australia); (3) confirmation of the two-stage Ge enrichment in the Barrigao deposit, with demonstration of the presence of Ge in solid solution in the early chalcopyrite (Portuguese Iberian pyrite belt); and (4) the enrichment of U during late dissolution-reprecipitation reactions in the bornite ores of the Moonta and Wallaroo IOCG deposits (South Australia). These results illustrate that MSXRF is a powerful technique for locating nano-to microparticles of precious metals (Pt) and trace contaminants (e.g., Hg) that form distinct (micro) minerals. In addition, it is a powerful tool for understanding commodities with relatively low ore grades and complex distribution (100.1,000 ppm; e.g., U, Ge).