This work presents the results of a 4-year study (2009–2012) investigating the mixing and photoreactivity of dissolved organic matter (DOM) in the Nelson/Hayes estuary (Hudson Bay). Dissolved organic carbon (DOC), colored DOM, and humic-like DOM decreased with increasing salinity (r2=0.70–0.84). Removal of DOM was noticeable at low to mid salinity range, likely due to degradation and/or adsorption to particles. DOM photobleaching rates (i.e., decrease in DOM signal resulting from exposure to solar radiation) ranged from 0.005 to 0.030h−1, corresponding to half-lives of 4.9–9.9days. Dissolved organic matter from the Nelson and Hayes Rivers was more photoreactive than from the estuary where the photodegradation of terrestrial DOM decreased with increasing salinity. Coincident with the loss of CDOM absorption was an increase in spectral slope S, suggesting a decrease in DOM molecular weight. Marked differences in photoreactivity of protein- and humic-like DOM were observed with highly humidified material being the most photosensitive. Information generated by our study will provide a valuable data set for better understanding the impacts of future hydroelectric development and climate change on DOM biogeochemical dynamics in the Nelson/Hayes estuary and coastal domain. This study will constitute a reference on terrestrial DOM fate prior to building additional generating capacity on the Nelson River.