This study delves into the intricate interplay between lithological characteristics and the morphometric attributes of 45 river sub-basins in Peninsular India. These sub-basins are geologically categorized into three distinct rock types: granitic gneiss, basalt, and limestone shale. The morphometric parameters scrutinized encompass infiltration number, ruggedness number, drainage texture, elongation ratio, circulatory ratio, and drainage frequency. Analysis of infiltration numbers reveals a substantial elevation, approximately 42%, in basaltic river sub-basins compared to their granitic gneiss and limestone counterparts. This disparity underscores heightened infiltration rates within basaltic terrains. Ruggedness numbers elucidate a remarkable 66% increase in the ruggedness of river sub-basins situated in granitic gneiss in contrast to those in basalt and limestone, highlighting the profound influence of lithological resistance on the topographical features. Circulatory ratios exhibit a 9% augmentation in river sub-basins entrenched within limestone shale rocks, while elongation ratios manifest a 3.5% advantage for basaltic river sub-basins. Drainage texture values indicate a substantial 50% rise in basaltic river sub-basins when juxtaposed with granitic gneiss and limestone. Furthermore, drainage frequency values elucidate a 3% ascent in basalt and limestone river sub-basins compared to granitic gneiss. This comprehensive analysis furnishes invaluable insights into lithology’s pivotal role in sculpting river basins’ morphometry. Basaltic terrains exhibit notably higher infiltration rates, reduced ruggedness, and heightened drainage texture values, while limestone shale regions demonstrate advantages regarding circulatory and elongation ratios. Understanding these intricate relationships is paramount for fostering sustainable water resource management and informed land use planning across Peninsular India.