Peatlands store 1/3 of global soil carbon, destabilisation of which contributes much to the recent increase in DOC (Dissolved Organic Carbon) in freshwater ecosystems. One suggested mechanism for the enhanced decomposition of peat and the releases of DOC is recovery from acidification. However, no biological role in the process has yet been identified. Here, we report extracellular enzyme activities and microbial composition in peatlands of Korea, the UK, Japan and Indonesia, and find higher pH to promote phenol oxidase activities, greater abundances in Actinobacteria and fungi, and enhanced pore-water DOC concentrations. Our pH manipulation experiments also showed that increase in pH enhanced phenol oxidase activity and DOC production with greater Actinobacterial and fungal abundances. Finally, knockout or addition of phenol oxidase dramatically changed DOC and phenolic production, indicating the central role of phenol oxidase in DOC mobilisation. Our findings provide evidence to support a previously unrecognized biological mechanism through which pH increases activate phenol oxidase, accelerating the release of DOC and phenolics.