Dissolved organic carbon (DOC) impacts water quality, the carbon cycle, and the ecology of aquatic systems. Understanding what controls DOC is therefore critical for improving large-scale models and best management practices for aquatic ecosystems. The two main processes of DOC transformation and removal, photochemical and microbial DOC degradation, work in tandem to modify and remineralize DOC within natural waters. Here, we examined both the photo- and microbial remineralization of DOC (photolability and biolability), and the indirect phototransformation of DOC into biolabile DOC (photoprimed biolability) for samples that capture the spatiotemporal and hydrological gradients of the Connecticut River watershed. The majority of DOC exported from this temperate watershed was photolabile and the concentration of photolabile DOC correlated with UV absorbance at 254 nm (r² = 0.86). Phototransformation of DOC also increased biolability, and the total photolabile DOC (sum of photolabile and photoprimed biolabile DOC) showed a stronger correlation with UV absorbance at 254 nm (r² = 0.92). We estimate that as much as 49% (SD = 3.3%) and 10% (SD = 1.1%) of annual DOC export from the Connecticut River is directly photolabile and photoprimable, respectively. Thus, 2.82 Gg C year⁻¹ (SD = 0.67 Gg C year⁻¹) or 1.13 Mg C km⁻² year⁻¹ (SD = 0.27 km⁻² year⁻¹) of total photolabile DOC escapes photochemical degradation within the river network to be exported from the Connecticut River each year.