Reflectance spectroscopy has been used to identify several deposit types. However, applications concerning lithium (Li)-pegmatites are still scarce. Reflectance spectroscopic studies complemented by microscopic and geochemical studies were employed in the Fregeneda–Almendra (Spain–Portugal) pegmatite field to analyze the spectral behavior of Li-minerals and field lithologies. The spectral similarity of the target class (Li-pegmatites) with other elements was also evaluated. Lepidolite was discriminated from other white micas and the remaining Li-minerals. No diagnostic feature of petalite and spodumene was identified, since their spectral curves are dominated by clays. Their presence was corroborated (by complementary techniques) in petalite relics and completely replaced crystals, although the clay-related absorption depths decrease with Li content. This implies that clays can be used as pathfinders only in areas where argillic alteration is not prevalent. All sampled lithologies present similar water and/or hydroxide features. The overall mineral assemblage is very distinct, with lepidolite, cookeite, and orthoclase exclusively identified in Li-pegmatite (being these minerals crucial targets for Li-pegmatite discrimination in real-life applications), while chlorite and biotite can occur in the remaining lithologies. Satellite data can be used to discriminate Li-pegmatites due to distinct reflectance magnitude and mineral assemblages, higher absorptions depths, and distinct Al–OH wavelength position. The potential use of multi- and hyperspectral data was evaluated; the main limitations and advantages were discussed. These new insights on the spectral behavior of Li-minerals and pegmatites may aid in new Li-pegmatite discoveries around the world.

The existence of diagnostic features in the visible and infrared regions makes it possible to use reflectance spectra not only to identify mineral assemblages but also for calibration and classification of satellite images, considering lithological and/or mineral mapping. For this purpose, a consistent spectral library with the target spectra of minerals and rocks is needed. Currently, there is big market pressure for raw materials including lithium (Li) that has driven new satellite image applications for Li exploration. However, there are no reference spectra for petalite (a Li mineral) in large, open spectral datasets. In this work, a spectral library was built exclusively dedicated to Li minerals and Li pegmatite exploration through satellite remote sensing. The database includes field and laboratory spectra collected in the Fregeneda–Almendra region (Spain–Portugal) from (i) distinct Li minerals (spodumene, petalite, lepidolite); (ii) several Li pegmatites and other outcropping lithologies to allow satellite-based lithological mapping; (iii) areas previously misclassified as Li pegmatites using machine learning algorithms to allow comparisons between these regions and the target areas. Ancillary data include (i) sample location and coordinates, (ii) sample conditions, (iii) sample color, (iv) type of face measured, (v) equipment used, and for the laboratory spectra, (vi) sample photographs, (vii) continuum removed spectra files, and (viii) statistics on the main absorption features automatically extracted. The potential future uses of this spectral library are reinforced by its major advantages: (i) data is provided in a universal file format; (ii) it allows users to compare field and laboratory spectra; (iii) a large number of complementary data allow the comparison of shape, asymmetry, and depth of the absorption features of the distinct Li minerals.