Many catchment management schemes in the UK have focussed on peatland restoration to improve ecosystem services such as carbon sequestration, water quality and biodiversity. The effect of these schemes on dissolved organic carbon (DOC) flux is critical in understanding peatland carbon budgets as well as the implications for drinking water treatment. In many catchments, however, peatland areas are not the only source of DOC, meaning that their significance at the full catchment scale is unclear. In this paper we have evaluated the importance of different land uses as sources of DOC by combining three datasets obtained from the Exe catchment, UK. The first dataset comprises a weekly monitoring record at three sites for six years, the second, a monthly monitoring record of 25 sites in the same catchment for one year, and the third, an assessment of DOC export from litter and soil carbon stocks. Our results suggest that DOC concentration significantly increased from the peaty headwaters to the mixed land-use areas (ANOVA F = 12.52, p < 0.001, df = 2), leading to higher flux estimates at the downstream sites. We present evidence for three possible explanations: firstly, that poor sampling of high flows may lead to underestimation of DOC flux, second, that there are significant sources of DOC besides the peatland headwaters, and finally, that biological- and photo-degradation decreases the influence of upstream DOC sources. Our results provide evidence both for the targeting of catchment management in peatland areas as well as the need to consider DOC from agricultural and forested areas of the catchment.