Labelling of meso-2,3-dimercaptosuccinic acid (DMSA) with technetium-99m was reinvestigated. Dependence of the 99mTc-DMSA complex formation on the molar ratio of DMSA:reducing agent (SnCl2·2H2O) and pH was studied. Five different types of 99mTc-DMSA complexes were determined. Especially three different complexes were established in the clinically used and prepared DMSA kit labelled with 99mTc under alkaline condition. This radiopharmaceutical is used as imaging agent of the primary medullary carcinoma in the thyroid gland and different metastasis types. The existence of all complexes was observed by paper chromatography, paper electrophoresis and high performance liquid chromatography.