Lithium-cesium-tantalum (LCT) pegmatites are widely distributed in northeastern, eastern, and central Afghanistan. The largest raremetal pegmatites having Lithium (Li)-bearing minerals occur in the Nuristan pegmatite belt in Eastern Afghanistan. The main aim of this study is to detect and highlight the Li-bearing pegmatites using spectral analysis within the Southwest Konar province in the east of Afghanistan and to establish self-proposed spectral indices for the detection of Li-rich minerals. To achieve the study’s objective, we apply several algorithms, for example, false color composite, band ratio, and spectral angle mapper on ASTER, Landsat 8 OLI/TIRS, and Sentinel-2MSI data. Considering the spectral characteristics of key mineral spodumene and other diagnostic minerals, for example, lepidolite, amblygonite, and cookeite, which are considered diagnostic minerals of LCT pegmatites, particularly lithium, we utilize the ECOSTRESS Spectral Library-Version 1.0 for the interpretation of reflectance and absorption determinants of these minerals. Based on the diagnostic characteristics of the selected Li-bearing minerals, we examine several BRs and thresholding and consequently, propose new spectral indices which show a high concentration of spodumene, cookeite, and lepidolite over the northern regions of the study area. According to the obtained results, ASTER data and thresholded BRs present effective results compared to Landsat 8 OLI/TIRS. Based on the final outputs, we define nine zones having Li-bearing pegmatites, particularly over the Chapa Dara and Dara-e-Pech districts of southwestern Konar province, which could be promising areas of interest for further detailed exploration. Lastly, we compare the 118 known Li-bearing points collected from previous studies and field observations with the newly-defined zones to validate accuracy. The study’s overall accuracy is 71.1%, indicating a good match between our findings and the reference points. [ABSTRACT FROM AUTHOR]