A suite of natural matrix reference materials (RMs) were used to assess the quality of analytical results obtained by k0-instrumental neutron activation analysis (k0-INAA) at the Joef Stefan Institute (IJS). Five certified reference materials (CRMs) from the Institute for Reference Materials and Measurements (IRMM), two standard reference materials (SRMs) from the National Institute of Standards and Technology (NIST), three RMs from the International Atomic Energy Agency (IAEA) and one RM from IJS were analyzed. Altogether, results for twenty-four elements in inorganic matrices and twenty-nine elements in organic matrices, obtained by k0-INAA, were compared to certified values. Results obtained show good agreement with certified or assigned values except for Fe, La, Nd, Sm and U in inorganic matrices, and Ag, Al and Cr in organic matrices.