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The carboxyl terminal of sodium oleate has a stronger polarity than that of oleic acid;this terminal is more likely to be dipole polarized and ionically conductive in a microwave ifeld. Sodium oleate was used as the model compound to study the decarboxylation of oleic acid leading to hydrocarbon formation via microwave-assisted pyrolysis technology. The pyrolysis gas, liquid, and solid products were precisely analyzed to deduce the mechanism for decarboxylation of sodium oleate. Microwave energy was able to selectively heat the carboxyl terminal of sodium oleate. During decarboxylation, the double bond in the long hydrocarbon chain formed a p-πconjugated system with the carbanion intermediate. The resulting p-πconjugated system was more stable and beneifcial to the pyrolysis reaction (decarboxylation, terminal allylation, isomeriza-tion, and aromatization). The physical properties of pyrolysis liquid were generally similar to those of diesel fuel, thereby demonstrating the possible use of microwaves for controlling the decarboxylation of sodium oleate in order to manufacture renewable hydrocarbon fuels.