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The fungal <jats:italic>Thermothelomyces thermophila<\/jats:italic> glucuronoyl esterase (TtGE) is a promising thermophilic enzyme that hydrolyses LCC ester bonds. This study describes the TtGE catalytic mechanism using QM\/MM methods. Two nearly\u2010degenerate rate\u2010determining transition states were found, with barriers of 16 and 17\u2005kcal\u2009\u22c5\u2009mol<jats:sup>\u22121<\/jats:sup>, both with a zwitterionic nature that results from a proton interplay from His346 to either the Ser213\u2010hydroxyl or the lignin leaving group and the rehybridisation of the ester moiety of the substrate to an alkoxide. An oxyanion hole, characteristic of esterases, was provided by the conserved Arg214 through its backbone and sidechain. 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