Deterioration of groundwater quality is a matter of serious concern today. In Mandla region of central India, fluorosis is common among the local people due to consumption of fluoride-contaminated groundwater. It is, therefore, important to understand the hydrochemical process of contamination and assess the groundwater quality of this region. A total of 173 samples (pre-monsoon and post-monsoon) were collected from borewells and dug wells of different depths for major ions analysis: K+, Na+, Ca2+, Mg2+, Cl−, CO32−, HCO3−, NO3−, SO42−, and F−; along with pH, temperature, TH (as CaCO3), TDS and EC. Broadly, three hydrogeologic units have been identified, viz. Deccan lava flows, infratrappean Lameta and Archean granite and gneiss. In Deccan, two distinct hydrostratigraphic units are Mandla and Dhuma. Mandla is the most prominent and extensive aquifer having hydraulic conductivity 5–15 mday-1 and yield 10–50 m3day−1. Water quality data vis-à-vis well-depth data indicate that Mandla aquifer, lying at a lower elevation than 500 m amsl, is fluoride-contaminated and harmful for human health. Fluoride (41.0% of total samples) and bicarbonate (54.9% of total samples) concentrations in analyzed water are above the global standard for drinking purpose. However, above 500 m msl groundwater is not contaminated with fluoride and is suitable for drinking and irrigation purpose. Fluoride concentration maps depict spatial and seasonal variation. Spatial variation of fluoride in groundwater is due to change in aquifer lithology, varying degree of rock weathering and orientation of structural lineaments. In fluoride concentration map of post-monsoon season, broadening of contour of uncontaminated zone indicates groundwater recharge, which corroborates with water fluctuation map. The fluoride-contaminated water and low-fluoride water are mainly Na–HCO3 and Ca–HCO3 type, respectively. The hydrochemical processes suggest pre-dominance of rock-water interaction; contribution of Na+ and K+ ions in groundwater is due to silicate weathering, whereas Ca2+ and Mg2+ ions are derived due to both silicate and carbonate weathering. Saturation index calculation point towards calcite-dolomite supersaturation and consequent precipitation, along with fluorite dissolution under alkaline condition.