Two ammonium decavanadate(V) compounds, (H 2 tmen) 3 V 10 O 28 Á6H 2 O (1) and (H 2 en) 3 V 10 O 28 Á2H 2 O (2), where H 2 tmen and H 2 en represent the doubly protonated N,N,N 0 ,N 0 -tetramethylethylenediammonium ion and doubly protonated ethylenediammonium ion, respectively, have been synthesized and structurally characterized by elemental analyses, spectroscopic (i.r., e.s.r.) studies, and single-crystal X-ray diffraction. Both crystal structures reveal the presence of the [V 10 O 28 ] 6-cluster anions, doubly protonated diammonium cations, and lattice water molecules. Hydrogen bonds assemble these two compounds to form three-dimensional networks. The in vitro anticancer activity against A549 and P388 tumor cells lines has also been determined by the MTT-based assay, and the results suggest that both compounds can inhibit proliferation of these two kinds of tumor cells.