The silica leached from coal fly ash using alkali, via the hydrothermal method, can be used as the raw material for the synthesis of xonotlite fibers through the hydrothermal synthesis method. This investigation was made to examine how the fly ash desilicated liquid influences the crystal growth and microstructure of xonotlite fibers. The obtained samples were characterized by X-ray diffraction and scanning electron microscope techniques to investigate their mineralogical composition and morphological characteristics. The results indicated that the pure desilication liquid leached from coal fly ash could be used to prepare xonotlite fibers. Xonotlite fibers with single crystal characteristics and large aspect ratio of 100–400 were successfully fabricated from fly ash desilication liquid, which is used as the silica material, at 240°C for 6 h.