Reaction of (MeC5H4)3Ln with HOCH2CH2NMe2 in tetrahydrofuran(THF) gives the new complexes [(MeC5H4)2Ln(μ-OCH2CH2NMe2)]2 (Ln=Sm, Y, Nd) with nitrogen functionalized μ-alkoxide ligand. The complexes were characterized by elemental analysis and IR, and [(MeC5H4)2Sm(μ-OCH2CH2NMe2)]2 was structurally characterized by the X-ray diffraction to be a dimer formed by two unsymmetric oxygen bridges. The complex has a tricyclic skeleton with the additional two Sm-N bonds via intramolecular coordination of OCH2CH2NMe2. The coordination number of the central metal Sm is nine. The title complexes show good catalytic activity for ring-opening polymerization of ε-caprolactone.