Reactionof(MeC5H4)3LnwithHOCH2CH2NMe2intetrahydrofuran(THF)givesthenewcomplexes[(MeC5H4)2Ln(μ-OCH2CH2NMe2)]2(Ln=Sm,Y,Nd)withnitrogenfunctionalizedμ-alkoxideligand.ThecomplexeswerecharacterizedbyelementalanalysisandIR,and[(MeC5H4)2Sm(μ-OCH2CH2NMe2)]2wasstructurallycharacterizedbytheX-raydiffractiontobeadimerformedbytwounsymmetricoxygenbridges.ThecomplexhasatricyclicskeletonwiththeadditionaltwoSm-NbondsviaintramolecularcoordinationofOCH2CH2NMe2.ThecoordinationnumberofthecentralmetalSmisnine.Thetitlecomplexesshowgoodcatalyticactivityforring-openingpolymerizationofε-caprolactone.