A denitrogenative palladium-catalyzed C(sp2)–C(sp2) cross-coupling of aryl-substituted diazenes capped with a trimethylsilyl group and functionalized aryl bromides is reported. A PEPPSI™ catalyst in the presence of NaOt-Bu enables the activation of the N-aryl-N’-silyldiazene pronucleophile with concomitant loss of dinitrogen and subsequent coupling of the in-situ-formed aryl nucleophile. By this, biaryl compounds bearing a variety of substituents can be prepared.