The oxyboration of arynes was achieved for the first time. A series of 2-aryl-1,3,2-dioxaborolane derivatives were reacted with aryne precursors in the presence of CsF to give the corresponding ring-expanded seven-membered borinic acid esters via selective boron-oxygen bond activation. Preliminary experimental mechanistic studies and density functional theory (DFT) calculations suggest that this unprecedented aryne oxyboration proceeds through the formation of boron ate complexes of arylboronates with CsF, followed by aryne insertion into the boron-oxygen bond.