Northern Chile, NW Argentina, and SW Bolivia, (“the lithium triangle”), represent a world class reservoir of lithium, but this extraordinary enrichment is still controversial, and different processes have been invoked over the years, including, geothermal waters associated with active volcanism, leaching of soluble salts from volcanic rocks and leaching of lithium-rich clays. The Salar de Atacama (SDA) represents one of the richest reservoirs of Li in northern Chile and has been extensively studied during the past years. Most of the studies have been focused in the southern and southeastern portions, where the highest lithium concentrations have been reported. However, a comprehensive model of water recharge at SDA is still imprecise. We used a combination of isotopic methods, including δ7Li, δ11B and 87Sr/86Sr ratios, with their chemical composition of a set of water samples from salt lakes, geothermal manifestations, groundwaters and surficial diluted waters (rivers and streams with low salinity). This study explores the hydrogeochemical processes controlling the water composition and solute distribution of the SDA. Our data confirm that weathering of the ignimbrites constitutes one of the most important processes in relation of solute origin in the region, where deep water-rock interactions would operate at high temperature, enhancing leaching of Li and other solutes. We determine that groundwater flow entering the SDA has undergone pre-enrichment processes (e.g., leak from Altiplano salt lakes; evaporite dissolution, among others) associated with salt inputs in the Western Cordillera. Our results provide a step forward to a comprehensive understanding of the processes that govern brine formation and lithium enrichment in a hyperarid environment, contributing to a sustainable exploration and exploitation of lithium in these environments.