Fine-grained garnet (grains <50 μm across) is an accessory component of compact hematite, a rock consisting essentially of hematite; compact hematite is a variety of high-grade Fe ore. The garnet is characterized compositionally as spessartine (81–86 mol.%) with subordinate, but significant, amounts of calderite (5–11 mol.%) and “blythite” (up to ~5 mol.%), as well as andradite (4–7 mol.%); pyrope and almandine endmembers are ≤~2 and 1 mol.%, respectively. The recognition of spessartine in compact hematite indicates that oxidation state, rather than whole-rock chemical composition, controlled the garnet composition. The spessartine has a positive Eu anomaly, and a low Th/U ratio (0.13–0.65) compared to the average upper continental crust, Th/U = 3.9, as well as a positive linear correlation of U vs. Li. The spessartine-hosting compact-hematite rock is a high-grade hematite ore that similarly shows a low Th/U ratio, but a convex, tetrad-like segment between Gd and Dy. Decoupling of Eu from other rare-earth elements and of U from Th in the spessartine, together with the anomalous geochemical behaviour of Gd, Tb and Dy in the compact hematite, and its low Th/U ratio, could have been achieved under oxidizing conditions at greenschist-facies metamorphic temperatures. The U and Li present in the spessartine could have been sourced from metamorphic fluids of continental, possibly evaporitic, origin. These interpretations are underpinned by the regional hematitization and tourmalinization observed in the southern Serra do Espinhaço.