Three tantalum oxyfluorides, with structures ranging from molecular cluster, molecular cage to polymeric chain, were synthesized by using organic cations as structure-directing agents in the presence of aqueous hydrofluoric acid. Single-crystal X-ray analysis reveals that compound [C7H13NH]6[Ta2OF10][Ta4O4F16]·(H2O)2 (1, C7H13NH = quinuclidinium) contains binuclear [Ta2OF10]2– and tetranuclear [Ta4F12O6]4– anions, compound [NH(C2H4)2NH2CH3][Ta6O9F18]·(H2O)3 (2, NH(C2H4)2NH2CH3 = doubly protonated 1- methyl-piperazine) contains the hexagonal cages of [Ta6O9F18]6–, and compound [C6H5NH3][TaOF4] (3, C6H5NH3 = anilinium) features a one-dimensional polymeric chain of [TaOF4]nn– in which oxygen atoms act as bridging ligands. Notably, compound 1 is the first tantalum oxyfluoride comprising mixed discrete anionic tantalum oxyfluoride clusters, while compound 2 features a rare molecular cage with a Ta6 trigonal prism structure.