The first piezochemically driven decarboxylative coupling of the C–H bond was developed. The agitation of BaTiO3 via ball milling converts mechanical energy into electrical potential, leading to the production of a benzoyl radical via a single-electron transfer pathway analogous to the photocatalytic reaction. This mechanoredox BaTiO3 catalytic strategy to synthesize C3-acylated quinoxalin-2(1H)-ones requires no solvent, a short reaction time, and simple handling skills, exhibiting promising potential in large-scale chemical manufacturing.