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This study focuses on characterizing the contributions of key terrestrial pathways that deliver dissolved organic carbon (DOC) to streams during hydrological events and on elucidating factors governing variation in water and DOC fluxes from these pathways. We made high‐frequency measurements of discharge, specific conductance (SC), and fluorescent dissolved organic matter (FDOM) during 221 events recorded over 2 years within four Vermont (USA) watersheds that range in area from 0.4 to 139 km². Using the SC measurements, together with statistical information on discharge, we separated the event hydrographs into contributions from three terrestrial pathways, which we refer to as riparian quickflow, subsurface quickflow, and slow‐flow groundwater. The pathway discharges were used as input to a mixing model that closely approximated sub‐hourly streamwater DOC concentrations as measured with the FDOM sensors. Subsurface quickflow, comprised of pre‐event water, was the leading contributor to streamwater DOC fluxes, while riparian quickflow, comprised of event water, was the second‐leading contributor to streamwater DOC fluxes, despite comprising the smallest proportion of streamflow yield among the three end‐member pathways. Fixed‐effects regression analysis revealed that the relationship between DOC fluxes from the end‐member pathways and event magnitude was consistent across the four watersheds. This analysis also showed that DOC fluxes from the quickflow pathways increased significantly with temperature and varied inversely, but weakly, with catchment antecedent wetness. We believe that our approach, which leverages in‐stream sensors that enable high‐frequency measurements over extended periods, may be applicable for evaluating controls on DOC export from other watersheds within and beyond our study region.