Depolymerisation of lignin to aromatics is a challenging task. We herein report that a Cu(OAc)2/BF3·OEt2 catalyst is eﬀective in simultaneously cleaving C–C bonds in β-1 and β-O-4 ketones, yielding esters and phenols. In-depth studies show that C–H bond activation is the rate determining step for C–C bond cleavage. BF3·OEt2 promotes the reaction via activating the β-C–H bond. This study oﬀers the potential to obtain aromatic esters from lignin.