In this work, single-phase ZSM-5 zeolite was synthesized using solid waste coal fly ash (CFA) as raw material, providing a potential alternative for creating high-value-added products from this waste. X-ray diffraction (XRD), scanning electron microscopy, X-ray fluorescence, Fourier transform infrared spectroscopy, N2 physisorption, and other techniques were used to evaluate the crystallization and morphology of the ZSM-5 obtained. The results indicated that ZSM-5 can be synthesized by the simple method of mixing, stirring, and heating. A well-defined hexagonal shape of ZSM-5 with a specific surface area of 162 m2/g and mesoporous structure was obtained at the temperature of 160 °C during hydrothermal treatment for 72 h. Theoretically, the mechanism of crystal growth of ZSM-5, i.e. the liquid phase nucleation and step growth models, was clarified. These results open the possibility of exploring the crystallization of ZSM-5 and the utilization of CFA. Simultaneously, the critical roles of silicon in framework formation and crystallization control during the formation and growth of zeolites were elucidated.