Photomineralization of terrigenous dissolved organic matter (tDOM) in the Arctic Ocean is limited by persistent sea ice cover that reduces the amount of ultraviolet (UV) radiation reaching the underlying water column. UV-dependent processes are likely to accelerate as a result of shrinking sea ice extent and decreasing ice thickness caused by climatic warming over this region. In this study, we made the first quantitative estimates of photomineralization of tDOM in a coastal Arctic ecosystem under current and future sea ice regimes. We used an optical-photochemical coupled model incorporating water column optics and experimental measurements of photoproduction of dissolved inorganic carbon (DIC), the main carbon product of DOM photochemistry. Apparent quantum yields of DIC photoproduction were determined on water samples from the Mackenzie River estuary, the Mackenzie Shelf, and Amundsen Gulf. UV irradiances just below the sea surface were estimated by combining satellite backscattered and passive microwave radiance measurements with a radiative transfer model. The mean annual DIC photoproduction between 1979 and 2003 was estimated as 66.5 ± 18.5 Gg carbon in the surface waters of the southeastern Beaufort Sea, where UV absorption is dominated by chromophoric dissolved organic matter discharged by the Mackenzie River. This value is equivalent to 10% of bacterial respiration rates, 8% of new primary production rates and 2.8 ± 0.6% of the 1.3 Tg of dissolved organic carbon (DOC) discharged annually by the Mackenzie River into the area. During periods of reduced ice cover such as 1998, the latter value could rise to 5.1% of the annual riverine DOC discharge. Under an ice-free scenario, the model predicted that 150.5 Gg of DIC would be photochemically produced, mineralizing 6.2% of the DOC input from the Mackenzie River. These results show that the predicted trend of ongoing contraction of sea ice cover will greatly accelerate the photomineralization of tDOM in Arctic surface waters.