A new hydrazone Schiff base ligand was condensed from 2-hydroxy-3-methoxybenzaldehyde and pyrimidine-4-carbohydrazide {H2L = (E)-N'-(2-hydroxy-3-methoxybenzylidene)pyrimidine-4-carbohydrazide}, which was used to assemble two new Dy2 complexes Dy2L2(DMF)2(NO3)2 (1) and Dy2L2(DMF)2(AcO)2 (2). Notably, the coordinated anions have a subtle effect on the coordination configurations of the Dy3+ ions and the magnetic properties of the two Dy2 complexes. The Dy3+ ions in 1 and 2 have the same N2O5 coordination environment but show the triangular dodecahedron and the biaugmented trigonal prism coordination configurations, respectively. Magnetic measurements revealed that both 1 and 2 have intramolecular ferromagnetic interactions between the Dy3+ ions and show single-molecule magnet behaviors at 0 Oe, with Ueff/k values of 58.2 K for 1 and 59.9 K for 2. These magnetic properties may be explained by theoretical calculations.