Large-river deltaic estuaries and adjacent continental shelves have experienced multiple phases of transgressions and regressions to form interlayered aquifer-aquitard systems and are expected to host vast paleo-terrestrial groundwater hundreds of kilometres offshore. Here, we used offshore hydrogeology, marine geophysical reflections, porewater geochemistry, and paleo-hydrogeological models, and identified a previously unknown offshore freshened groundwater body with a static volume up to 575.6 ± 44.9 km3in the Pearl River Estuary and adjacent continental shelf, with the freshwater extending as far as 55 km offshore. An integrated analysis of stable isotopic compositions and water quality indices reveals the meteoric origins of such freshened groundwater and its significance as potential potable water or raw water source for desalination. Hotspots of offshore freshened groundwater in large-river deltaic estuaries and adjacent continental shelves, likely a global phenomenon, have a great potential for exploitable water resources in highly urbanized coastal areas suffering from freshwater shortage.