Soils export large amounts of organic matter to rivers, and there are still major uncertainties concerning the composition and reactivity of this material and its fate within the fluvial network. Here we reconstructed the pattern of movement and processing of dissolved organic matter (DOM) along a soil‐stream‐river continuum under summer baseflow conditions in a boreal region of Québec (Canada), using a combination of fluorescence spectra, size exclusion chromatography and ultrahigh resolution mass spectrometry. Our results show that there is a clear sequence of selective DOM degradation along the soil‐stream‐river continuum, which results in pronounced compositional shifts downstream. The soil‐stream interface was a hot spot of DOM degradation, where biopolymers and low molecular weight (LMW) compounds were selectively removed. In contrast, processing in the stream channel was dominated by the degradation of humic‐like aromatic DOM, likely driven by photolysis, with little further degradation of either biopolymers or LMW compounds. Overall, there was a high degree of coherence between the patterns observed in DOM chemical composition, optical properties, and molecular profiles, and none of these approaches pointed to measurable production of new DOM components, suggesting that the DOM pools removed during transit were likely mineralized to CO2. Our first order estimates suggest that rates of soil‐derived DOM mineralization could potentially sustain over half of the measured CO2 emissions from this stream network, with mineralization of biopolymers and humic substances contributing roughly equally to these fluvial emissions.