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Based on a multidentate Schiff-base ligand, N,N′-bis(2-hydroxy-5-methyl-3-formylbenzyl)-N,N′-bis-(pyridin-2-ylmethyl)ethylenediamine (H2L), two binuclear DyIII compounds, with formulas [Dy2(L)(NO3)3(CH3O)] (1) and [Dy2(L)(NO3)3(CH3CH2O)] (2), have been synthesized under different solvent systems. The DyIII ions in 1 and 2 adopt monocapped square antiprism coordination geometries, while different structural distortions can be observed. The two DyIII ions in 1 and 2 are bridged by two phenoxide atoms of one L2− ligand and one bridged CH3O−/CH3CH2O− oxygen node, leading to an approximate fusiform Dy2O3 core. The different DyIII–Obridged node distances, DyIII–Obridged node–DyIII angles and DyIII⋯DyIII distances can be observed. Magnetic studies reveal that 1 and 2 display slow magnetic relaxation behaviours under a zero direct-current field with the effective energy barriers (Ueff) of 114.17 K and 171.23 K, respectively. Furthermore, compound 2 possesses the highest Ueff in nine-coordinated Dy2 compounds. The M versus H data exhibit weak butterfly-shaped hysteresis loops at 2 K for 2. The rare CH3O−/CH3CH2O−-bridged nine-coordinated binuclear DyIII single-molecule magnets (SMMs) significantly regulate and enhance the Ueff of compounds 1 and 2. To deeply understand their different magnetic behaviours, the magnetic anisotropies and magnetic interactions of 1 and 2 were studied by ab initio calculations. These findings demonstrate an efficient approach for regulating and enhancing the magnetic anisotropy barriers using a bridged CH3O− anion or CH3CH2O− anion. [ABSTRACT FROM AUTHOR]