Changes in hydrological regimes due to rapid urbanization and increasing anthropogenic stress on hydro-geological system creating an alarming condition for the management of ground water resources. Isotope and hydro-geochemical integrated approach has been used to determine the processes governing chemical composition of groundwater and the mechanism influencing the chemical composition of groundwater in National Capital Region (NCR), Delhi. The chemical evolution of groundwater has studied by using flow direction, hydro-chemical facies, bivariate plots of ionic ratios and saturation index. Stable isotopes and tritium are used to understand the recharge mechanism. Pollution index of groundwater (PIG) is also used to check the level of contamination in the groundwater. In total, 57 water samples were collected for water chemistry, 36 water samples for environmental isotopes and 13 samples for tritium measurement. The dominant water type is Ca-Mg-HCO3 and mixed water type. The dominant cation are Ca2+ > Na+ > Mg2+ > K+ and dominant anions are HCO3− > Cl− > SO42− > NO3−. The bicarbonate type water is dominant in quartzite, implies rapid and direct recharge through fracture and joints. Ionic ratios and saturation indices show that major processes controlling groundwater evolution are silicate hydrolysis and reverse cation exchange in the quartzite. Average values of δ2H and δ18O are −43.66 ‰ and −6.28‰. Stable isotopic ratio of groundwater of alluvium area falling on evaporation line, due to the prevailing semi-arid and arid climatic conditions, evaporation is the predominant factor affecting the chemistry of groundwater. The stable isotope shows that the groundwater in the quartzite is mostly meteoric in origin and acting as a recharge area for the nearby alluvium aquifer. Tritium results reveal that groundwater occurring in quartzite and alluvium aquifer in western parts are older than that of groundwater occurring in alluvium aquifer in the eastern parts.13% of groundwater samples are falling in very high pollution zone mainly occurring in alluvium aquifer that lies in the Eastern parts. It is inferred that alluvium aquifer (low lying) is having greater impact of anthropogenic activity than quartzite aquifer (high land).