The Sm–Nd isotopic system has been broadly utilized for dating and tracing in earth and planetary sciences. However, low Nd+ ionization efficiency permanently hinders precise and accurate measurements on small amounts of Nd samples. So far, isotopic measurement of micro-amount Nd sample via thermal ionization mass spectrometry (TIMS) Nd+ mode was mostly performed on Nd reference solutions, but less on natural rock or mineral samples. In the present study, analytical procedures to measure isotopic composition via the TIMS Nd+ mode were designed for natural rock powders by using 1–5 ng pure Nd. The analytical technique was refined through low-blank sample digestion, small-column chemistry for Nd extraction from matrix elements, loading Nd using purified H3PO4 solution, and careful heating of filaments before data acquisition. Measurements on small Nd amounts (1 ng–5 ng) of either the JNdi-1 reference solution or four reference rock powders yielded satisfactory results of 143Nd/144Nd value with respect to precision and accuracy. The analytical results agree well with the recommendation values of the reference materials within analytical errors and the internal precision is better than ±0.005 % (2RSE). When using 1 ng or 2 ng Nd amounts, 144Nd ion flow can remain stable in a signal intensity of >100 mV, and without the assistance of an additional ionization enhancer. Therefore, the analytical procedure, featured by low procedural blank (about 10–22 pg), high Nd+ ionization efficiency, and easy operation, has broad prospects for the application of Nd isotope in single-grain minerals or micro-samples.