This study investigates the impact of Earth's core formation on the metal–silicate partitioning of Sm and Nd, two rare-earth elements assumed to be strictly lithophile although they are widely carried by the sulphide phases in reducing material (e.g. enstatite chondrites). The partition coefficients of Sm and Nd (DSmDSm and DNdDNd) between molten CI and EH chondrites model compositions and various Fe-rich alloys (in the Fe–Ni–C–Si–S system) have been determined in a multi-anvil between 3 and 26 GPa at various temperatures between 2073 and 2440 K, and at an oxygen fugacity ranging from 1 to 5 log units below the iron–wüstite (IW) buffer. The chemical compositions of the run products and trace concentrations in Sm and Nd elements were determined using electron microprobe and laser ablation inductively coupled plasma-mass spectrometry. Our results demonstrate the non-fractionation of Sm and Nd during the segregation of the metallic phases: the initial Sm/Nd ratio of about 1 in the starting materials yields precisely the same ratio in the recovered silicate phases after the equilibration with the metal phases at all conditions investigated in this study. In addition, DSmDSm and DNdDNd values range between 10−310−3 and 10−510−5 representing a low solubility in the metal. An increase of the partition coefficients is observed with decreasing the oxygen fugacity, or with an increase of S content of the metallic phase at constant oxygen fugacity. Thus, based on the actual Sm and Nd concentrations in the bulk Earth, the core should contain less than 0.4 ppb for Sm and less than 1 ppb for Nd. These estimates are three orders of magnitude lower than what would be required to explain the reported 142Nd excess in terrestrial samples relative to the mean chondritic value, using the core as a Sm–Nd complementary reservoir. In other words, the core formation processes cannot be responsible for the increase of the Sm/Nd ratio in the mantle early in Earth history.