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Abstract We characterized the dissolved organic matter (DOM) under baseflow conditions from a set of rivers in the Mohawk and Hudson River watersheds. The rivers in this study drain a range of bedrock geologies and land cover. We identify how those factors influence riverine DOM reactivity and the source, age, and composition of the biolabile DOM. We performed laboratory incubation experiments to characterize each river's reactive and non‐reactive DOM pools. Measurements of dissolved organic carbon concentration, radiocarbon, Ultraviolet‐visible spectroscopy absorbance, and Fourier‐transform ion cyclotron resonance mass spectrometry (FTICR‐MS) analysis were performed at each incubation start and end, allowing us to determine the quantity, age, and composition of the reactive and nonreactive DOM pools. We find that lithology controls bulk DOM ages, with watersheds underlain by shale/limestone having the most aged DOM and crystalline/metasedimentary watersheds having the youngest DOM. We observe that for a given lithology, bulk DOM age increases with the proportion of agricultural land in the watershed–suggesting agricultural practices mobilize aged DOM. FTICR‐MS analysis reveals that both lithology and land cover influence DOM composition. Shale/limestone watersheds showed DOM compositions distinct from other watershed lithologies, and the percentage of nitrogen‐containing DOM correlated with agricultural influence. In two of the studied rivers we find that the biolabile DOM fraction is older than the bulk DOM (upwards of 7 kyr) revealing that aged DOM may be preferentially consumed in these rivers. Our findings provide insight into how riverine carbon cycles may respond to watershed disturbances that influence DOM inputs to rivers.