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Certifications of trace elements in existing CRMs, especially biological CRMs, are far from satisfactory. Neutron activation analysis (NAA) for its inherent advantages combined with newly established parametric standardization, may contribute to improve this situation. The continuing progress of the hybrid extended k0-relative NAA technique developed in our laboratory is discussed. Examples are given to show the reliability of the method in certification of multielements. RNAA is still one of the best methods, or even the method of choice, in analysis at sub-μg/g concentration levels. The suitability of the technique for this purpose has been studied through the determination of rare earth elements at ng/g concentration level in two Chinese biological CRMs using both RNAA and ICPMS. Sampling behaviors of multielements in CRMs have been studied by INAA in an effort to develop CRMs suitable for analysis with small sample sizes.