Radiochemical neutron activation analysis was used for determinations of 8 rare earth elements (La, Ce, Nd, Sm, Eu, Tb, Yb and Lu) in two Chinese CRMs, GBW 08503 (wheat) and GBW 09101 (hair), and Cs, Sr, Th and U in five NIST SRMs, 1548 (Total Diet), 1486 (Bone Meal), 8414 (Bovine Muscle), 1566a (Oyster Powder) and 1575 (Pine Needles). These determinations are for eventual certification of above ultratrace elements so far not certified. The radiochemical separation scheme used in RNAA of NIST SRMs is an anion exchange followed by the co-precipitation by (REE)F3 for U and Th, and a SrSO4 precipitation for Sr and Cs. For RNAA of the two Chinese CRMs, a one step (REE)F3 precipitation was used. Chemical yields were determined for all relevant elements by tracer experiments. All these materials were also analyzed by ICPMS, that offered an opportunity to compare the two major trace analytical techniques on their merits and drawbacks for these particular cases. RNAA is proven to be one of the important techniques in ultratrace analysis, especially in certification of some ultratrace elements. Determination of elements in sub-ng/g level is still an area to be further investigated because: (1) some such elements are important in food and health related environmental studies, (2) many of these elements have no (or very few) certified values in existing biological CRMs, (3) reliable techniques qualified for ultratrace analysis are needed to be established, and (4) sampling behavior of elements at these levels is still not very well known (recommended minimum sample size may not be adequate).