The interaction between surface water and groundwater is not only an important part of the water cycle, but also the foundation of the study on regional water resources quantity. The field hydrogeological investigation and sampling in the Liujiang basin were conducted in the dry season, in April, 2015. The isotopic ratios of hydrogen and oxygen and ion compositions as well as the hydrogeochemical characteristics indicated that the groundwater in the basin was mainly HCO₃-Ca and HCO₃-Ca·Mg type low salinity water. The groundwater of each region had a unified connection, experiencing the same or similar hydrochemical formation, and the surface water had the same hydrochemical type and source of hydrochemical composition as groundwater. The hydrogen and oxygen isotopic compositions of surface water and groundwater were close to each other, which were mainly from the atmospheric precipitation. In the runoff process, the river water was affected by the evaporation concentration so that the heavy isotopes were slightly enriched. Under the influence of topographical, geological and hydrogeological conditions, the interaction between groundwater and surface water in the basin had obvious segmentation and mutual transformation. The river was recharged by both sides of groundwater in upstream region of Dashi River and Donggong River basin while river water supplied groundwater on both sides of it in downstream region of Dashi River.