By virtue of a calcium(II)/hexafluoroisopropanol cocatalytic system, the efficient and practical coupling of 3-aminobenzoic acids with alkynes has been realized, giving direct and regioselective access to the phthalide framework with good substrate/functional group compatibility. Mechanistic studies identified 3-amino-2-vinylbenzoic acid species as the active intermediate, thereby revealing an ortho-C-alkenylation/hydroacyloxylation cascade for this transformation.