Global warming can substantially affect the export of dissolved organic carbon (DOC) from peat-permafrost to aquatic systems. The direct degradability of such peat-derived DOC, however, is poorly constrained because previous permafrost thaw studies have mainly addressed mineral soil catchments or DOC pools that have already been processed in surface waters. We incubated peat cores from a palsa mire to compare an active layer and an experimentally thawed permafrost layer with regard to DOC composition and degradation potentials of pore water DOC. Our results show that DOC from the thawed permafrost layer had high initial degradation potentials compared with DOC from the active layer. In fact, the DOC that showed the highest bio- and photo-degradability, respectively, originated in the thawed permafrost layer. Our study sheds new light on the DOC composition of peat-permafrost directly upon thaw and suggests that past estimates of carbon-dioxide emissions from thawed peat permafrost may be biased as they have overlooked the initial mineralization potential of the exported DOC.