A series of triylenes of the heavy group 13 elements gallium, indium and thallium, carrying the pentaisopropylcyclopentadienyl ligand is reported. The compounds were characterized in solution and in the solid‐state and their donor ligand properties in heterobimetallic complexes were investigated, whereby a series of tungsten carbonyl complexes was isolated. Furthermore, a new synthetic route towards a previously described lithium‐aluminum heterobimetallic dimetallocene is reported, which also enabled the isolation of a heterobimetallic polydecker of lithium and gallium.