A reliable determination of natural and anthropogenic radionuclides in environmental samples is necessary to comply with the radiation protection and environmental regulations. This paper presents the results of the characterisation of massic activities of natural and anthropogenic radionuclides in soil and water matrices produced as test items to conduct the proficiency test ERAD-PT-2013. The proficiency test ERAD-PT-2013 was designed to investigate analytical performance in analysing both natural and anthropogenic radionuclides, to assist laboratories to identify analytical problems, and to improve the quality of measurement results. The proficiency test items, their spectral interferences and the activity concentration levels of the analytes were designed in a way to enable identification of potential analytical problems. Methodologies, data evaluation approach and evaluation of proficiency test results for each radionuclide are described and discussed.