The formation of decavanadates containing amine counter-ions is explored to get a better insight into the resulting crystal packing. From mixtures containing the Schiff base H 2 (SO 3 -sal) 2 en and vanadate, two different compounds containing decavanadate units have been characterised by X-ray diffraction. The structure of 1 consists of [V 10 O 28 ] 6− monomers united by K + , ethylenediamine cations and H 2 O molecules, which act as bridging atoms between the layers, forming a three-dimensional array. The structure of 2 contains vanadium triprotonated decavanadate anions, [H 3 V 10 O 28 ] 3− , in one-dimensional vertical chains, bonded by interdecavanadate hydrogen bonds. The interchain region is populated by (H 2 en) 2+ cations and H 2 O molecules, which form a network of hydrogen bonds. From the filtrate solution of the reaction mixture containing V IV OSO 4 , d,l-diaminopropionic acid and salicylaldehyde, which also contained triethylamine, a diprotonated decavanadate 3 was obtained. Compound 3 consists of decavanadate vertical dimers, surrounded by triethylamonium cations that preclude the interaction between the dimers. Bond valence calculations were used to confirm the degree of protonation of the decavanadate anions.