Extensive new data from previously unstudied Siberian streams and rivers suggest that mobilization of currently frozen, high-latitude soil carbon is likely over the next century in response to predicted Arctic warming. We present dissolved organic carbon (DOC) measurements from ninety-six watersheds in West Siberia, a region that contains the world's largest stores of peat carbon, exports massive volumes of freshwater and DOC to the Arctic Ocean, and is warming faster than the Arctic as a whole. The sample sites span ∼106 km2 over a large climatic gradient (∼55–68°N), providing data on a much broader spatial scale than previous studies and for the first time explicitly examining stream DOC in permafrost peatland environments. Our results show that cold, permafrost-influenced watersheds release little DOC to streams, regardless of the extent of peatland cover. However, we find considerably higher concentrations in warm, permafrost-free watersheds, rising sharply as a function of peatland cover. The two regimes are demarcated by the position of the −2°C mean annual air temperature (MAAT) isotherm, which is also approximately coincident with the permafrost limit. Climate model simulations for the next century predict near-doubling of West Siberian land surface areas with a MAAT warmer than −2°C, suggesting up to ∼700% increases in stream DOC concentrations and ∼2.7–4.3 Tg yr−1 (∼29–46%) increases in DOC flux to the Arctic Ocean.