The reaction of the potassium 1,3-trisilanediide Me₂Si[Si(Me₃Si)₂K]₂ with SmI₂ and YbI₂ was found to give the respective disilylated complexes Me₂Si[Si(Me₃Si)₂]₂Sm·2THF and Me₂Si[Si(Me₃Si)₂]₂Yb·2THF. Desolvation of coordinated solvent molecules in these complexes made their handling difficult. However, using a number of functionalized silanide ligands, complexes with a diminished number or even no coordinated solvent molecules were obtained ((R₃Si)₂Ln(THF)_x (x = 0–3)). The structures of all new lanthanide compounds were determined by X-ray single-crystal structure analysis. NMR spectroscopic analysis of some Yb–silyl complexes pointed at highly ionic interactions between the silyl ligands and the lanthanides. This bonding picture was supported by DFT calculations at the B3PW91/Basis1 level of theory. Detailed theoretical analysis of a disilylated Eu(II) complex suggests that its singly occupied molecular orbitals (SOMOs) are very close in energy to the ligand silicon lone pairs (HOMO), and SQUID magnetometry measurements of the complex showed a deviation from the expected behavior for a free Eu(II) ion, which might be due to a ligand–metal interaction.