Considering water as a limiting factor for socio-economic development, especially in arid/semi-arid regions, both scientific communities and policymakers are interested in groundwater recharge-related data. India is fast moving toward a crisis of groundwater due to intense abstraction and contamination. There is a lack of understanding regarding the occurrence, movement, and behaviors of groundwater in a fractured basement terrane. Therefore, integrated environmental isotopes (δ18O, δ2H, and 3H) and hydrogeochemical studies have been used to understand the recharge processes and geochemical evolution of groundwater in the fractured basement terranes of Gujarat, NW India. Our results show that the relative abundance of major cations and anions in the study basin are Ca2+ > Na+ > Mg2+ > K+ and HCO3− > Cl− > SO42− > NO3−, respectively. This suggests that the chemical weathering of silicate minerals influences the groundwater chemistry in the aquifer system. A change in hydrochemical facies from Ca-HCO3 to Na-Mg-Ca-Cl. HCO3 has been identified from the recharge to discharge areas. Along the groundwater flow direction, the presence of chemical constituents with different concentrations demonstrates that the various geochemical mechanisms are responsible for this geochemical evolution. Furthermore, the chemical composition of groundwater also reflects that the groundwater has interacted with distinct rock types (granites/granulites). The stable isotopes (δ18O and δ2H) of groundwater reveal that the local precipitation is the main source of recharge. However, the groundwater recharge is affected by the evaporation process due to different geological conditions irrespective of topographical differences in the study area. The tritium (3H) content of groundwater suggests that the aquifer is mainly recharged by modern rainfall events. Thus, in semi-arid regions, the geology, weathering, and geologic structures have a significant role in bringing chemical changes in groundwater and smoothening the recharge process. The findings of this study will prove vital for the decision-makers or policymakers to take appropriate measures to design water budgets as well as water management plans more sustainably.