Reaction of ferrocene with lithium in the presence of either ethylene or COD allows the Fe(0)-ate complexes 1 and 4 to be prepared on a large scale, which turned out to be excellent catalysts for a variety of Alder-ene, [4+2], [5+2], and [2+2+2] cycloadditon and cycloisomerization reactions of polyunsaturated substrates. The structures of ferrates 1 and 4 in the solid-state reveal the capacity of the reduced iron center to share electron density with the ligand sphere. This feature, coupled with the kinetic lability of the bound olefins, is thought to be responsible for the ease with which different enyne or diyne substrates undergo oxidative cyclization as the triggering event of the observed skeletal reorganizations. This mechanistic proposal is corroborated by highly indicative deuterium labeling experiments. Moreover, it was possible to intercept two different products of an oxidative cyclization manifold with the aid of the Fe(+1) complex 6, which, despite its 17-electron count, also turned out to be catalytically competent in certain cases. The unusual cyclobutadiene complex 38 derived from 6 and tolane was characterized by X-ray crystallography.