Little attention has thus far been paid to the potential effect of solution composition on the hydrothermal crystallization of calcium sulfate whiskers prepared from flue-gas desulfurization (FGD) gypsum. When purified FGD gypsum was used as raw material, the morphology and phase structure of the hydrothermal products grown in pure water, H2SO4–H2O, NaCl–H2O, and H2SO4–NaCl–H2O solutions as well as the solubility of purified FGD gypsum in these solutions were investigated. The results indicate that calcium sulfate whiskers grow favorably in the H2SO4–NaCl–H2O system. When prepared using 10–70 g NaCl/kg gypsum −0.01 M H2SO4–H2O at 130 °C for 60 min, the obtained calcium sulfate whiskers had diameters ranging from 3 to 5 μm and lengths from 200 to 600 μm, and their phase structure was calcium sulfate hemihydrate (HH). Opposing effects of sulfuric acid and sodium chloride on the solubility of the purified FGD gypsum were observed. With the co-presence of sulfuric acid and sodium chloride in the reaction solution, the concentrations of Ca2+ and SO42− can be kept relatively stable, which implies that the crystallization of the hydrothermal products can be controlled by changing the concentrations of sulfuric acid and sodium chloride.