Syntheses and molecular structures of the first cyanate bridged lanthanide-transition metal complexes, (DMF)8Ln2Ni(NCO)8 and {(DMF)6Ln2Ni(NCO)8}∞ (Ln = Sm, Eu) with three bridging cyanate ligands are reported; magnetic properties of (DMF)8Ln2Ni(NCO)8 (Ln = Sm, Eu) complexes are described.