Abstract Clusters of dipole charge-carrier capture centers were studied in anthracene crystals doped with carbazole. The microscopic model for the dipole centers of the different structure is proposed. The thermoluminescence of the anthracene crystal doped with carbazole was investigated in the temperature range of 4.2–300 K. It was shown that thermoluminescence bands became structured with the increase of the impurity concentration. The observed structure is explained by the emergence of dipole charge-carrier capture centers created by clusters of impurities, which consist of one, two or more molecules. The authors carried out theoretical calculations both for immobile carriers and taking into account their delocalisation. The theoretical results are in good agreement with experimental ones.