The traditional preparation of ZSM-5 molecular sieves relies on chemical reagents to provide silicon and aluminum sources, which are limited as raw materials and cannot be commonly used in production practice. Using coal gangue as the raw material and using medium-temperature chlorination roasting and the pressure acid leaching process to control the silicon–aluminum ratio [n(Si/Al)] of coal gangue, a ZSM-5 molecular sieve was prepared using the alkali melting hydrothermal method. The pressure acid leaching process solved the limitation that kaolinite and mica cannot simultaneously be activated. Under optimal conditions, the n(Si/Al) of the coal gangue increased from 6.23 to 26.14 and complied with the requirements for the synthesis n(Si/Al) of a ZSM-5 molecular sieve. The effect of n(Si/Al) on the preparation of the ZSM-5 molecular sieve was studied. Finally, spherical granular ZSM-5 molecular sieve material with a microporous specific surface area of 169.6329 m2/g, an average pore diameter of 0.6285 nm, and a pore volume of 0.0988 cm3/g was prepared. Providing ideas for the high-value utilization of coal gangue, it is significant for solving the problem of coal gangue solid waste, as well as the problem of ZSM-5 molecular sieve feed stock.