Three new MOFs with the same components but different structures and magnetic behavior, {[Cu6(atr)6(H2O)2(μ3 OH)2(SO4)5 ]·5.25H2O} n (1), {[Cu2(atr)2( -OH)2(SO4 )]·3H2O} n (2), and {[Cu7(atr)6(H2O)6(μ3-OH)2(SO4 )6 ]·2H2O} n (3) (atr = 4-amino-1,2,4-triazole), were respectively synthesized by diffusion reactions in the presence of different structure-directing agents. Complex 1 is a slightly spin-frustrated antiferromagnetic layer with sulfonate aggregated CuⅡ6 clusters periodically extended by ditopic sulfonate linkers. 2 is a grid-based coplanar sheet with hydroxyl group bridgedCuOCulinear-chain interlinked by pairs of μ3 -atr ligands, exhibiting strong antiferromagnetic interactions to lead to an S = 0 spin ground state at low temperature. In contrast, air-instable 3 has a ladder-like broad-ribbon structure constructed from triangular CuⅡ3 cores and centrosymmetric CuⅡ1 octahedra. Obviously, the variable CuⅡ -ligand connectivity and the involving magnetic properties are significantly dominated by the cooperative and variable binding modes of the mixed sulfonate-atr ligands and bi-/tridentate bridging hydroxyl heterobridges. Three new MOFs with the same components but different structures and magnetic behavior, {[Cu6 (atr) 6 (H2O) 2 (μ3OH) 2 (SO4) 5] · 5.25H2O} n (1) 2 (SO4) 6 · 2H2O} n (2) and {[Cu7 (atr) 6 (H2O) 6 (μ3-OH) 2 = 4-amino-1,2,4-triazole, were also synthesized synthetically by diffusion reactions in the presence of different structure-directing agents. Complex 1 is a slight spin-frustrated antiferromagnetic layer with sulfonate aggregated Cu II 6 clusters Period extended by ditopic sulfonate linkers. 2 is a grid-based coplanar sheet with hydroxyl group bridged Cuuulinear-chain interlinked by pairs of μ3-atr ligands, exhibiting strong antiferromagnetic interactions to lead to an S = 0 spin ground state at low temperature. In contrast, air-instable 3 has a ladder-like broad-ribbon structure constructed from triangular Cu II 3 cores and centrosymmetric Cu II octahedra. Obviously, the variable Cu Ⅱ -ligand connectivity and the involving magnetic properties are significantly dominated by the cooperative and variable binding modes of the mixed sulfonate-atr ligands and bi- / tridentate bridging hydroxyl heterobridges.