The chemical complexity of decomposing plant litter is a central feature shaping the terrestrial carbon (C) cycle, but explanations of the origin of this complexity remain contentious. Here, we ask: How does litter chemistry change during decomposition, and what roles do decomposers play in these changes? During a long-term (730 days) litter decomposition experiment, we tracked concurrent changes in decomposer community structure and function and litter chemistry using high-resolution molecular techniques. Contrary to the current paradigm, we found that the chemistry of different litter types diverged, rather than converged, during decomposition due to the activities of decomposers. Furthermore, the same litter type exposed to different decomposer communities exhibited striking differences in chemistry, even after > 90% mass loss. Our results show that during decomposition, decomposer community characteristics regulate changes in litter chemistry, which could influence the functionality of litter-derived soil organic matter (SOM) and the turnover and stabilisation of soil C.