Two unprecedented wheel-shaped nanoscale clusters {Co(II)16Ln(III)24} (Ln = Dy and Gd), with a diameter and a thickness of 3.0 nm and 2.0 nm, respectively, were obtained from the self-assembly of Co(NO3)2, Ln(NO3)3 and a pyridyl-functionalized β-diketone ligand. Notably, the gadolinium species exhibited a relatively large magnetocaloric effect.