The rare-earth metal hydroxylamide compound Y[N(SiHMe2)2]2[ONBn2][THF] (1) was prepared by the silylamide elimination pathway from the reaction of N,N-dibenzylhydroxylamine, Bn2NOH (Bn = CH2C6H5), with Y[N(SiHMe2)2]3[THF]2 and was characterised by multinuclear NMR spectroscopy and elemental analysis. The compounds [Cp2Y(ONBn2)]2 (2a) [Cp2Sm(ONBn2)]2 (2b) were obtained by the reactions of MCp3 (M = Y, Sm) with Bn2NOH. The trinuclear compound Cp5Y3[ON(Me)CH2CH2(Me)NO]2 (3) was obtained by the reaction of YCp3 and the bishydroxylamine HON(Me)CH2CH2(Me)NOH. 2a, 2b and 3 were characterised by NMR spectroscopy, single-crystal X-ray diffraction and elemental analysis. In all these complexes side-on-coordination of the hydroxylamide units was observed. The compounds are of dynamic nature in solution.