Arsenic (As) contamination in groundwater is a worldwide concern for drinking water safety. Environmental changes and anthropogenic activities are making groundwater vulnerable in Pakistan, especially in Central Punjab. This study explores the distribution, hydrogeochemical behavior, and pathways of As enrichment in groundwater and discusses the corresponding evolution mechanism, mobilization capability, and health risks. In total, 510 groundwater samples were collected from three tehsils in the Punjab province of Pakistan to analyze As and other physiochemical parameters. Arsenic concentration averaged 14.0 μg/L in Vehari, 11.0 μg/L in Burewala, and 13.0 μg/L in Mailsi. Piper-plots indicated the dominance of Na+, SO42−, Ca2+, and Mg2+ ions in the groundwater and the geochemical modeling showed negative saturation indices with calcium carbonate and salt minerals, including aragonite (CaCO3), calcite (CaCO3), dolomite (CaMg(CO3)2), and halite (NaCl). The dissolution process hinted at their potential roles in As mobilization in groundwater. These results were further validated with an inverse model of the dissolution of calcium-bearing mineral, and the exchange of cations between Ca2+ and Na+ in the studied area. Risk assessment suggested potential carcinogenic risks (CR > 10−4) for both children and adults, whereas children had a significant non-carcinogenic risk hazard quotient (HQ > 1). Accordingly, children had higher overall health risks than adults. Groundwater in Vehari and Mailsi was at higher risk than in Burewala. Our findings provide important and baseline information for groundwater As assessment at a provincial level, which is essential for initiating As health risk reduction. The current study also recommends efficient management strategies for As-contaminated groundwater.