Three-coordinate bipyridyl complexes of gold, (κ2-bipy)­Au­(η2-C2H4)­NTf2, are readily accessed by direct reaction of 2,2′-bipyridine (bipy), or its derivatives, with the homoleptic gold ethylene complex Au­(C2H4)3­NTf2. The cheap and readily available bipyridyl ligands facilitate oxidative addition of aryl iodides to the Au­(I) center to give (κ2-bipy)­Au­(Ar)­I­NTf2, which undergo first aryl-zinc transmetalation and second C–C reductive elimination to produce biaryl products. The products of each distinct step have been characterized. Computational techniques are used to probe the mechanism of the oxidative addition step, offering insight into both the origin of the reversibility of this process and the observation that electron-rich aryl iodides add faster than electron-poor substrates. Thus, for the first time, all steps that are characteristic of a conventional intermolecular Pd­(0)-catalyzed biaryl synthesis are demonstrated from a common monometallic Au complex and in the absence of directing groups.