The South Pole–Aitken (SPA) basin, located between the South Pole and Aitken crater on the far side of the Moon, is the largest confirmed lunar impact structure. The pre-Nectarian SPA basin is a 2400 × 2050 km elliptical structure centered at 53°S, 191°E, which should have exposed lower crust and upper mantle due to the enormous excavation depth. Olivine, the dominant mineral in Earth’s mantle, has only been identified in small and localized exposures in the margins of the SPA basin, and the dominant mafic component is, instead, pyroxene. These mineralogical characteristics could be explained by the recent hypothesis that the lunar upper mantle is dominated by low-calcium pyroxene, not olivine. Here, we present observations from imaging and spectral data from China’s Chang’E-4 (CE-4) lunar mission in the first 4 synodic days, especially the first in situ visible/near-infrared spectrometer observations of an exposed boulder. We identified a variety of rock types, but not the recently reported olivine-rich materials in the landing region. The results are consistent with orbital observations. The obtained mineralogical information provides a better understanding of the nature and origin of SPA materials.