Two supramolecular nickel-organic frameworks, [Ni(HBTC)(bix)]n (1) and [Ni3(BTC)2(mbix)3(H2O)4]n · 6nH2O (2) (bix = 1,4-bis(imidazole-l-yl-methyl)benzene, mbix = 1,3-bis(imidazole-l-yl-methyl)benzene, and H3BTC = 1,3,5-benzenetricarboxylate), have been hydrothermally prepared by the assembly of H3BTC, Ni2+ with bix or mbix. Compound 1 shows a 2D layer structure, whose 3D supramolecular structure exhibits a fsc topology when hydrogen-bonging interactions between the adjacent layers are taken into account. Compound 2 manifests an unprecedented 2D (3, 4)-connected topological net. The 3D supramolecular framework of 2 is formed through π⋯π stacking interactions between the adjacent layers. The magnetic studies show that 1 features overall ferromagnetic property whilst 2 presents strong zero-field splitting (ZFS) when treated as a mononuclear model. Furthermore, the IR and TGA properties of 1 and 2 were also studied.Two supramolecular nickel-organic frameworks, [Ni(HBTC)(bix)]n (1) and [Ni3(BTC)2(mbix)3(H2O)4]n · 6nH2O (2) (bix = 1,4-bis(imidazole-l-yl-methyl)benzene, mbix = 1,3-bis(imidazole-l-yl-methyl)benzene, and H3BTC = 1,3,5-benzenetricarboxylate), were obtained under hydrothermal reactions. The 3D supramolecular structure of compound 1 exhibits a rarely encountered 3D (4, 6)-connected fsc topological net when hydrogen-bonging interactions between the adjacent layers are taken into account. Compound 2 manifests an unprecedented 2D (3, 4)-connected topological net. Close π⋯π stacking interactions occur between the adjacent layers of compound 2. The magnetic studies show that compound 1 features overall ferromagnetic property. Whereas compound 2 was treated as a mononuclear model, which presents strong zero-field splitting (ZFS). Furthermore, the IR and TGA properties of 1 and 2 were also studied.