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Recognition of biochar as a potential tool for long-term carbon sequestration with additional agronomic benefits is growing. However, the functionality of biochar in soil and the response of soils to biochar inputs are poorly understood. It has been suggested, for example, that biochar additions to soils could prime for the loss of native organic carbon, undermining its sequestration potential. This work examines the priming potential of biochar in the context of its own labile fraction and procedures for their assessment. A systematic set of biochar samples produced from C4 plant biomass under a range of pyrolysis process conditions were incubated in a C3 soil at three discrete levels of organic matter status (a result of contrasting long-term land management on a single site). The biochar samples were characterised for labile carbon content ex-situ and then added to each soil. Priming potential was determined by a comparison of CO₂ flux rates and its isotopic analysis for attribution of source. The results conclusively showed that while carbon mineralisation was often higher in biochar amended soil, this was due to rapid utilisation of a small labile component of biochar and that biochar did not prime for the loss of native organic soil organic matter. Furthermore, in some cases negative priming occurred, with lower carbon mineralisation in biochar amended soil, probably as a result of the stabilisation of labile soil carbon.