Artificial intelligence (AI)-based multispectral remote sensing has been the best supporting tool using limited resources to enhance the lithological mapping abilities with accuracy, supported by ground truthing through traditional mapping techniques. The availability of the dataset, choice of algorithm, cost, accuracy, computational time, data labeling, and terrain features are some crucial considerations that researchers continue to explore. In this research, support vector machine (SVM) and artificial neural network (ANN) were applied to the Sentinel-2 MSI dataset for classifying lithologies having subtle compositional differences in the Kohat Basin’s remote, inaccessible regions within Pakistan. First, we used principal component analysis (PCA), minimum noise fraction (MNF), and available maps for reliable data annotation for training SVM and (ANN) models for mapping ten classes (nine lithological units + water). The ANN and SVM results were compared with the previously conducted studies in the area and ground truth survey to evaluate their accuracy. SVM mapped ten classes with an overall accuracy (OA) of 95.78% and kappa coefficient of 0.95, compared to 95.73% and 0.95 by ANN classification. The SVM algorithm was more efficient concerning computational efficiency, accuracy, and ease due to available features within Google Earth Engine (GEE). Contrarily, ANN required time-consuming data transformation from GEE to Google Cloud before application in Google Colab.