The underlying reactivity of Au-III-F species with aryl boronic acids has been studied in detail taking advantage of four novel, stable difluoro-[((CN)-N-boolean AND)AuF2], arylmonofluoro-[((CN)-N-boolean AND)AuArF], and alkylmonofluoro-[((CN)-N-boolean AND)AuAlkF] gold(III) complexes, prepared and isolated in monomeric form. We provide the first experimental evidence for a direct Au-III-F/B transmetalation preceding the Csp(2)-Csp(2) or Csp(3)-Csp(2) bond formation.