We report the synthesis of three neutral complexes with different coordination modes of a di-silylated metalloid germanium cluster to divalent lanthanides [(thf) 5 Ln(η n -Ge 9 (Hyp) 2 )] (Ln = Yb (1, n = 1); Eu (2, n = 2, 3), Sm (3, n = 2, 3); Hyp = Si(SiMe 3 ) 3 ) by the salt metathesis of LnI 2 with K 2 [Ge 9 (Hyp) 2 ] in THF. The complexes were characterized by elemental analysis, nuclear magnetic resonance and UV−vis−NIR spectroscopy, and single-crystal X-ray diffraction. In thf solution, the formation of contact or solvate-separated ion pairs depending on the concentration is assumed. Compound 2 exhibits a blue luminescence typical for Eu 2+ . The solid-state magnetic measurements of compounds 2 and 3 confirm the presence of divalent europium and samarium, respectively.