The first dynamic model of dissolved organic carbon (DOC) export in streams derived directly from high frequency (sub-hourly) observations sampled at a regular interval through contiguous storms is presented. The optimal model, identified using the recently developed RIVC algorithm, captured the rapid dynamics of DOC load from 15-minute monitored rainfall with high simulation efficiencies and constrained uncertainty with a second-order (two-pathway) structure. Most of the DOC export in the four headwater basins studied was associated with the faster hydrometric pathway (also modelled in parallel), and was soon exhausted in the slower pathway. A delay in the DOC mobilisation became apparent as the ambient temperatures increased. These features of the component pathways were quantified in the dynamic response characteristics (DRCs) identified by RIVC. The model and associated DRCs are intended as a foundation for a better understanding of storm-related DOC dynamics and predictability, given the increasing availability of sub-hourly DOC concentration data.