Three 2D heterospin radical-3d–4f networks with the formula {[Ln(hfac)3]2[M(hfac)2](NIT-3Py-5-Pyoe)2}n (MII = CoII and LnIII = Gd 1, Dy 2; MII = CuII and LnIII = Dy 3; NIT-3Py-5-Pyoe = (2-(5-(4-pyridinone)-3-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide)) have been successfully constructed using a novel multidentate nitronyl nitroxide paramagnetic ligand containing mixed N- and O-donor sites. In these 2D structures, the paramagnetic ligand acts as a tridentate linker to bind two LnIII ions by means of one aminoxyl group and one pyridinone unit and one MII ion through the pyridine ring. The magnetic behaviors of 1–3 are governed by predominant ferromagnetic radical–Ln interactions.