The nature of trapping and emission centers in Mn‐ and Pb‐activated calcite (CaCO3) is investigated with respect to thermoluminescence (TL) and optical absorption, between 77 and 750 K, after 253.7 nm UV‐ and X‐irradiation, using single crystals grown by hydro‐thermal method. Mn is responsible for the emission band at 620 nm, Pb at 300 nm; another, very weak, emission is observed about 450 nm. The importance of colour centres for the TL process in calcite is discussed. Comparisons are made with natural as well as other synthetic crystals.