Divalent β-diketiminate lanthanide complexes LYbR(THF)(L={(2,6-Me2C6H3)NC(Me)}2CH;R=C9H7(1),CH3C5H4(2),OC6H2-But2-2,6-Me-4(32))were synthesized by reducing the mixed-ligand trivalen(t) β-diketiminate ytterbium chlorides synthesized in situ with Na-K alloy.These divalent lanthanide complexes exhibit good catalytic activity for the ring opening polymerization of ε-caprolactone.