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Saudi Arabia is an arid country with very limited water resources. The absence of surface water bodies along with erratic rainfall renders groundwater as the most reliable source of potable water in arid and semi-arid regions globally. Groundwater quality is determined by aquifer characteristics regional geology and it is extensively influenced by both natural and anthropogenic activities. In the recent past, several methodologies have been adopted to analyze the quality of groundwater and associated hydro-geochemical process i.e., multivariate statistical analysis, geochemical modelling, stable isotopes, a redox indicator, structural equation modelling. In the current study, statistical methods combined with geochemical modelling and conventional plots have been used to investigate groundwater and related geochemical processes in the Aseer region of Saudi Arabia. A total of 62 groundwater samples has been collected and analyzed in laboratory for major cations and anions. Groundwater in the study region is mostly alkaline with electrical conductivity ranging from 285-3796 S/cm. The hydro-geochemical characteristics of groundwater are highly influenced by extreme evaporation. Climatic conditions combined with low rainfall and high temperature have resulted in a highly alkaline aquifer environment. Principal component analysis (PCA) yielded principal components explaining 79.9% of the variance in the dataset. PCA indicates ion exchange, soil mineralization, dissolution of carbonates and halite are the major processes governing the groundwater geochemistry. Groundwater in this region is oversaturated with calcite and dolomite while undersaturated with gypsum and halite which suggests dissolution of gypsum and halite as major process resulting into high chloride in groundwater. The study concludes that the combined approach of a multivariate statistical technique, conventional plots and geochemical modelling is effective in determining the factors controlling the groundwater quality.