The Orientale basin is a multiring impact structure on the western limb of the Moon that provides a clear view of the primary lunar crust exposed during basin formation. Previously, near-infrared reflectance spectra suggested that Orientale's Inner Rook Ring (IRR) is very poor in mafic minerals and may represent anorthosite excavated from the Moon's upper crust. However, detailed assessment of the mineralogy of these anorthosites was prohibited because the available spectroscopic data sets did not identify the diagnostic plagioclase absorption feature near 1250 nm. Recently, however, this absorption has been identified in several spectroscopic data sets, including the Moon Mineralogy Mapper (M3), enabling the unique identification of a plagioclase-dominated lithology at Orientale for the first time. Here we present the first in-depth characterization of the Orientale anorthosites based on direct measurement of their plagioclase component. In addition, detailed geologic context of the exposures is discussed based on analysis of Lunar Reconnaissance Orbiter Narrow Angle Camera images for selected anorthosite identifications. The results confirm that anorthosite is overwhelmingly concentrated in the IRR. Comparison with nonlinear spectral mixing models suggests that the anorthosite is exceedingly pure, containing >95 vol % plagioclase in most areas and commonly ~99–100 vol %. These new data place important constraints on magma ocean crystallization scenarios, which must produce a zone of highly pure anorthosite spanning the entire lateral extent of the 430 km diameter IRR.