Hierarchical HZSM-5 with tunable acidity, zeolitic crystallinity, and porosity were prepared using different organosilanes and used for the production of aromatics from the catalytic fast pyrolysis (CFP) of rice straw. As the chain length of organosilanes changed, the composition of the products including aromatics and coke varied greatly. Additionally, the introduction of ammonium ions into organosilanes led to a lower yield of aromatics and a higher yield of coke. Transmission electron microscopy, temperature-programmed desorption of NH3, N-2 adsorption-desorption (Brunauer-Emmett-Teller), and X-ray diffraction were used to explore the influence of the morphological structure, acidity distribution, textural properties, and crystallinity on the CFP of rice straw. The results indicated that the crystallinity, textural properties, and total acidity had a great influence on the synthesis of aromatics.