Two 2p-3d-4f complexes of [LnCu(hfac)5NIT-Ph-p-OCH2trz]n (Ln = Gd (1), Ho (2); NIT-Ph-p-OCH2trz = 2-(4-((1H-1,2,4-triazol-1-yl)methoxy)phenyl)-4,4,5,5-tetra- methylimidazoline-1-oxyl-3-oxide; hfac = hexafluoroacetylacetonate) have been successfully synthesized through Cu(hfac)2 and Ln(hfac)3 reacting with nitronyl nirtroxide radical of NIT-Ph-p-OCH2trz. The structures of complexes 1 and 2 were elucidated by single-crystal X-ray structural analysis and the results show that both complexes consist of [Ln-NIT-Ln-NIT]n one-dimensional chains and the additional Cu ions are coordinated to the nitrogen atoms from the triazole rings of the radical ligands. The ferromagnetic couplings are observed between the coordinated NO group and Ln (III) ions. Ac magnetic susceptibilities indicate that the Ho derivatives displays frequency-dependent out-of-phase signals.