A series of organically templated vanadium selenites has been prepared under mild hydrothermal conditions. Single crystals of [C5H14N2][(VO)(3)(SeO3)(2)(HSeO3)(4)], [C5H14N2][VO(SeO3)(2)], [(R)-C5H14N2][(VO)(3)(SeO3)(2)(HSeO3)(4)], and [(S)-C5H14N2][(VO)(3)(SeO3)(2)(HSeO3)(4)] were grown from VOSO4, SeO2, and 2-methylpiperazine. Controlling the initial pH of the reaction mixture allows for one to select between the compounds found in the VOSO4/SeO2/(2)-methylpiperazine system, as the solution pH directly affects the relative ratio of the HSeO3- and SeO32- concentrations. Moreover, partial resolution of racemic 2-methylpiperazine is observed in [C5H14N2][(VO)(3)(SeO3)(2)(HSeO3)(4)], which is understood through the use of a one-dimensional Ising model. The use of enantiomerically pure 2-methylpiperazine results in fully ordered and fully resolved structures.