Sorption of europium(III) on calcite from aqueous solution was investigated by kinetics and sorption isotherms at 323 K and by site-selective and time-resolved luminescence spectroscopy at 15 K. Three sorption sites (A, B, C) were characterized by this last technique. B constitutes a major family which appears in all samples with sorbed Eu and is characterized by an environment involving water or hydroxyl ions. The C family is observed only for the highest Eu concentrations. In these sites, the environment is more hydrated than in sites B. Site A constitutes a minority but appears in all samples. It corresponds to the centrosymmetric structural Ca site of calcite in position 2b, thus demonstrating that sorbed Eu(III) can substitute for Ca in calcite.