The combined use of 2-(2-pyridyl)-1,3-propane-diol (pypdH2) and 2-hydroxymethyl-2-(2-pyridyl)-1,3-propane-diol (pyptH3) in Cu2+/4f chemistry has afforded a new family of isostructural [Cu6M4(pypt)4(pypdH)4(NO3)8] [M = Gd (1), Tb (2), Dy (3), and Y (4)] complexes. These compounds are based on an unprecedented three-layered symmetric [Cu6M4(μ-OR)16]8+ structural core, formed from the connection of the metal ions by bridging alkoxide arms of the organic ligands. Direct current magnetic susceptibility studies for complexes 1-3 revealed the presence of dominant ferromagnetic exchange interactions, suggesting the existence of large spin ground state values. Alternating current magnetic studies indicate the presence of slow-magnetic relaxation in 1-3.