The modification of cyclopentadienyl ligands withcarefully selected substituents is a widely used strategy for tuning theirsteric and electronic properties. We describe the synthesis of anextremely bulky penta-terphenyl cyclopentadienyl ligand (CpT5)byarylation of cyclopentadiene. Deprotonation reactions with variousgroup 1 metals and bases afforded a complete series of alkali metalsalts MCpT5(M = Li-Cs). The compounds were isolated as solvate-free salts, which were characterized by multinuclear nuclear magneticresonance spectroscopy, ultraviolet-visible spectroscopy, and ele-mental analysis. Single-crystal X-ray diffraction studies of LiCpT5,NaCpT5(crystallized as a solvate with one tetrahydrofuran moleculeper formula unit), and KCpT5revealed the formation of metallocene-like sandwich structures in the solid state.