There is widespread recognition that the groundwater-surface water interface can have significant influence on the pattern and form of the transfer of nutrient-rich groundwater to rivers. Characterizing and quantifying this influence is critical for successful management of water resources in many catchments, particularly those threatened by rising nitrate levels in groundwater. Building on previous experimental investigations in one such catchment: the River Leith, UK, we report on a multimeasurement, multiscale program aimed at developing a conceptualization of groundwater-surface water flow pathways along a 200 m reach. Key to this conceptualization is the quantification of vertical and horizontal water fluxes, which is achieved through a series of Darcian flow estimates coupled with in-stream piezometer tracer dilution tests. These data, enhanced by multilevel measurements of chloride concentration in riverbed pore water and water-borne geophysical surveying, reveal a contrast in the contribution of flow components along the reach. In the upper section of the reach, a localized connectivity to regional groundwater, that appears to suppress the hyporheic zone, is identified. Further downstream, horizontal (lateral and longitudinal) flows appear to contribute more to the total subsurface flow at the groundwater-surface water interface. Although variation in hydraulic conductivity of the riverbed is observed, localized variation that can account for the spatial variability in flow pathways is not evident. The study provides a hydrological conceptualization for the site, which is essential for future studies which address biogeochemical processes, in relation to nitrogen retention/release. Such a conceptualization would not have been possible without a multiexperimental program.