Four new oxovanadium(IV) tartrates, namely, A(2)[(VO)(2)(C4H4O6)(C4H2O6)(H2O)(2)]center dot(H2O)(2), where A = Cs, 1, Rb, 2; K-2[(VO)(2)(C4H2O6)(2)(H2O)(2)]center dot(H2O)(2), 3; and Na2[(VO)(2)(C4H4O6)(C4H2O6)(H2O)7]center dot(H2O)(2), 4, were prepared utilizing a two-step, mild hydrothermal route involving l-(+)-tartaric acid as the reducing agent. All four compounds were structurally characterized by single-crystal and powder X-ray diffraction methods and were found to crystallize in the non-centrosymmetric orthorhombic space groups P2(1)2(1)2(1) for 1, 2, and 4 and C222(1) for 3. The temperature dependence of the magnetic susceptibility of these compounds was measured, and 1, 2, and 4 were found to be paramagnetic down to 2 K, while 3 was found to exhibit spin-dimer behavior. Compounds 1, 2, and 3 were found to be second harmonic generation active. All compounds were further characterized by IR and UV-vis spectroscopies.