The interaction of methoxyethyl functionalized indene compounds (C9H6-1-R-3-CH2CH2OMe, R=t-BuNHSiMe(1), Me3Si (2), H (3)) with [(Me3Si)2N]3Ln(μ-Cl)Li(THF)3 (Ln=Yb (4), Eu (5)) produced a series of new ytterbium (Ⅱ) and europium (Ⅱ) complexes via tandem silylamine elimination/homolysis of the Ln-N (Ln=Yb, Eu) bond.Treatment of the lanthanide (Ⅱ) amides [(Me3Si)2N]3Ln(μ-Cl)Li(THF)3 (Ln=Yb (4), Eu (5) with 2 equiv. of 1, 2and 3, respectively, produced, after workup, the ytterbium (Ⅱ) complexes [η5:η1-Me2Si(MeOCH2CH2C9H5)(NHBu-t)]2-YbII (6), (η5:η1-MeOCH2CH2C9H5SiMe3)2YbII (7), (η5:η1-MeOCH2CH2C9H6)2YbII (8) and the correspondingeuropium (Ⅱ) complexes [η5:η1-Me2Si(MeOCH2CH2C9H5)(NHBu-t)]2EuII (9), (η5:η1-MeOCH2CH2C9H5SiMe3)2EuII (10) and (η5:η1-MeOCH2CH2C9H6)2EuII (11) in moderate to good yield. In contrast, interaction of the corresponding indene compounds 1, 2 or 3 with the lanthanide amides [(Me3Si)2N]3Ln (Ln = Yb, Eu) was not observed, while addition of 0.5 equiv. of anhydrous LiCl to the corresponding reaction mixture produced, after workup, the corresponding ytterbium (Ⅱ) or europium (Ⅱ) complexes. All the new compounds were fully characterized by spectroscopic and elemental analyses. The structures of complexes 7, 9 and 10 were determined by single-crystal X-ray analyses. The catalytic activity of all the ytterbium (Ⅱ) and europium (Ⅱ) complexes on MMA polymerization was examined. It was found that all the ytterbium (Ⅱ) and europium (Ⅱ) complexes can function as single-component MMA polymerization catalysts. The temperature, solvent and ligand effects on the catalytic activity were studied.