The Xikuangshan antimony mine located at Central Hunan, China, is the largest antimony deposit in the world. Hydrothermal calcites from the Xikuangshan Mine display relatively large variations in REE abundance and Sm/Nd ratios and are characterized by MREE- and HREE-enriched and LREE-depleted patterns. Sm–Nd isotopic compositions of syn-sulfide calcites fall on well-defined lines in the isochron plot. Calcites from early- and late-stage mineralization form two distinct isochrons corresponding to 155.5±1.1 and 124.1±3.7 Ma, respectively. The isochron ages suggest that Sb mineralization took place during the Late Jurassic–Early Cretaceous Period in the Xikuangshan district, consistent with previous geological observations and with independent isotope data. Samarium–neodymium dating of calcites shows potential for determining ages of hydrothermal mineralization.