Lithological classification is essential for understanding the spatial distribution of rocks, especially in arid crystalline areas. Artificial intelligence (AI) recent advancements with multi-spectral satellite imagery have been utilized to enhance lithological mapping in these areas. Here we employed different AI models namely, Support Vector Machine (SVM), Random Forest Classification (RFC), Logistic Regression, XGBoost, and K-nearest neighbors (KNN) for lithological mapping. This was followed by the application of explainable AI (XAI) for lithological discrimination (LD) which is still not widely explored. Based on the highest accuracy and F1 score of the previously mentioned models, RFC model outperformed all of them, and hence, it was integrated with XAI, using the SHapley Additive exPlanations (SHAP) method.This approach successfully identified critical multi-spectral features for LD in arid crystalline zones when applied on the Landsat-8, Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER), and SRTM-DEM datasets covering the Hammash and the Wadi Fatimah areas in Egypt and the Kingdom of Saudi Arabia, respectively. Field validation in the Hammash area confirmed the RFC model's efficacy, achieving a satisfactory 94% overall accuracy for 18 features. SHAP was able to identify the top ten features for proper LD over the Hammash area with 90.3% accuracy despite the complex nature of the ophiolitic mélange. For validation purposes, RCF was then utilized in the Wadi Fatimah region, using only the top 10 critical features rendered from the SHAP analysis. It performed well and had 93% accuracy. Notably, XAI/SHAP results indicated that elevation data, Landsat-8's Green Band (B3), and the two ASTER SWIR bands (B5 and B6) were essential and significant for identifying island arc rocks. Moreover, the SHAP model effectively delineated complex mélange matrices, primarily using ASTER SWIR band (B8). Our findings highlight the successful combination of RFC with XAI for LD and its potential utilization in similar arid crystalline environments worldwide.