Abstract Ferrocenyllithium, FcLi (1), reacts with (C5H4CH3)2TiCl2, CpTiCl, and Cp*TiCl 3 to give the new σ-ferrocenyl complexes (C5H4CH3)2TiFc2 (2), CpTiFc3 (3) and Cp*Ti(Fc)2Cl (4), respectively. Treatment of Cp*2ZrCl2 with FcLi yields the mono-substitution product Cp*2Zr(Fc)Cl (5), which has been characterized by an X-ray structure analysis. Compound 5 crystallizes in the monoclinic space group P21/c (a = 1622.3(6), b = 995.0(2), c = 1664.3(6) pm; β = 94.78(3)°; Z = 4). Due to the sterically demanding pentamethylcyclopentadienyl ligands 5 contains a long zirconium-carbon bond (231.4(8) pm) and the Cp rings of the ferrocenyl substituent are tilted by 10.2°. The syntheses of CpZrFc3 (6), Cp*HfFc3 (7) and Cp2VFc2 (8) are also described.