The syntheses of two noncentrosymmetric (NCS) vanadium oxide-fluoride compounds that originate from the same synthetic reagent concentrations are presented. Hydrothermal and low-temperature syntheses allow the isolation of metastable products that may form new phases (or decompose) upon heating and allow creation of chemically similar but structurally different materials. NCS materials synthesis has been a long-standing goal in inorganic chemistry: in this article, we compare two chemically similar NCS inorganic materials, NaVOF(4)(H(2)O) (I) and NaVO(2-x)F(2+x) (II; x = 1/3). These materials originate from the same, identical reagent mixtures but are synthesized at different temperatures: 100 °C and 150 °C, respectively. Compound I crystallizes in Pna2(1): a = 9.9595(4) Å, b = 9.4423(3) Å, and c = 4.8186(2) Å. Compound II crystallizes in P2(1): a = 6.3742(3) Å, b = 3.5963(2) Å, c = 14.3641(7) Å, and β = 110.787(3)°. Both materials display second-harmonic-generation activity; however, compound I is type 1 non-phase-matchable, whereas compound II is type 1 phase-matchable.