XanI2 (4,5‐diiodo‐2,7‐di‐tert‐butyl‐9,9‐dimethylxanthene) and DBFI2 (4,6‐diiododibenzofuran) have been functionalized first with Ph2Bi units through reaction with PhLi and then with Ph2BiCl. The remaining C–I bonds were shown to undergo oxidative additions to M(PPh3)2 species (M = Pd, Ni; generated from employed [M(PPh3)4]), thus giving rise to heterometallic systems [Xan(BiPh2)Pd(PPh3)2I] (2), [Xan(BiPh2)Ni(PPh3)2I] (3), and [DBF(BiPh2)Pd(PPh3)2I] (6), where the bismuthane moieties are positioned vis‐à‐vis a d8‐MII center; treatment of 2 with AgOTf led to an exchange of the iodide ligand at the central nickel atom by a more weakly bound triflate ligand. The developed synthetic strategy can be envisioned to also provide access to combinations of such transition metal moieties with other main group entities for cooperative substrate activation. [ABSTRACT FROM AUTHOR]