Present herein is a stepwise assembly method toward aluminum-lanthanide-based (Al-Ln) compounds. From the perspective of charge balance, polyanions are necessary to bind with Ln ions. However, the synthesis of polyanions aluminum compounds remains quite challenging. Herein, two Al-4 polyanions [Al-4(L)(4)(Cat)(2)].4Hdma (AlOC-13, H3L= 2,3-dihydroxybenzoic acid, Cat = catechol, and dma = dimethylamine) and [Al4(L)(4)(HL)(2)(DMF())2].4Hdma.0.5DMF.0.5H2O (AlOC-14, DMF = N,N-dimethylformamide) were successfully obtained under solvothermal conditions. Catechol and Hdma were generated from the in situ decarboxylation of H3L ligand and decomposition of DMF, respectively. AlOC-13 is qualified for further coordination assembly for the available vacancy coordination sites, good water solubility, and scale-up synthesis. The assembly of Al4 polyanions with equivalent Ln ions afforded a series of zigzag chain structures [LnAl(4)(L)(4)(Cat)(2)(DMF)(2)(H2O)(3)].Hdma (Ln = Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb) (AlOC-13-Ln). Moreover, the magnetic behavior and photoluminescence of the series of AlOC-13-Ln were also studied. AlOC-13-Dy shows obvious antiferromagnetic behavior, while AlOC-13-Tb exhibits excellent green characteristic luminescence. This study not only paves the way toward anionic aluminum clusters but also reveals their potential application in water treatment of cationic metal ions capture.