Stoichiometric hydrates of Li 3 VO 4 , the hexahydrate and two polymorphs of the octahydrate, were prepared by evaporation of alkaline aqueous solutions 1 molar in LiOH and 0.5 molar in the metavanadate LiVO 3 at r. t. with or without the addition of Lithium sulfide, i. e. at different pH values. Their crystal structures have been determined and refined using single crystal X-ray data; all lithium and hydrogen atom positions were localised and refined without contraints. All three title compounds crystallise in non-centrosymmetric space groups. The water molecules belong to the tetrahedral coordination spheres of the Li cations, i. e. they are embedded as water of coordination exclusively. The tetrahedral orthovanadate(V) anions VO 3− 4 and the LiO 4 tetrahedra are connected via common O corners to form building units which are further held together by strong, nearly linear hydrogen bonds. The hexahydrate Li 3 VO 4 ・ 6H 2 O (space group R3, a = 962.9(2), c = 869.2(2) pm, Z = 3, R1 = 0.0260) contains isolated orthovanadate(V) anions VO 3− 4 surrounded by a 3D network of cornersharing Li(H 2 O) 4 tetrahedra forming rings of three, seven and eight units. The water molecules are ‘isolated’ in the sense that no hydrogen bonds are formed between water molecules. The octahydrate is dimorphous: The triclinic polymorph of Li 3 VO 4 ・ 8H 2 O (space group P1, a = 592.6(2), b = 651.3(2), c = 730.2(4) pm, α = 89.09(2), β = 89.43(2), γ = 88.968(12)°, Z = 1, R1 = 0.0325) contains two types of chains of tetrahedra: One consists of corner-sharing Li(H 2 O) 4 tetrahedra only, the second one is formed by alternating LiO 4 and VO 4 tetrahedra, also sharing oxygen corners. Only one water molecule is ‘isolated’, the other seven form a branched fragment of a chain with hydrogen bonds between them. In the monoclinic form of Li 3 VO 4 ・8H 2 O (space group Pc, a = 732.6(1), b = 653.7(1), c = 1292.9(3) pm, β = 112.21(1)°, Z = 2, R1 = 0.0289) a fragment of a chain of three LiO 4 tetrahedra, two of which share a common edge, and one VO 4 tetrahedron represent the formular unit. These building blocks are connected via hydrogen bonds formed by three ‘isolated’ water molecules and a chain fragment of five connected water molecules.