Even though tremendous progress has been made on modified Fischer-Tropsch synthesis (FTS) multifunctional catalyst that composed of Fe-based component and acidic zeolite H-ZSM-5 for CO2 hydrogenation into value-added chemicals, the structure-function relationship between the acidic zeolite H-ZSM-5 and product distribution is still under debate. Herein, a series of H-ZSM-5 zeolites with different Al locations and acidic properties are fabricated by varying the synthesis raw agents and conditions. After combining with the carbon-encapsulated Fe-based catalyst for alkenes synthesis from CO2 hydrogenation, aromatics are directionally produced from the ellipsoidal H-ZSM-5 with Al species mainly located at the intersection of straight and sinusoidal channels, while the main products shift to iso-paraffins for the H-ZSM-5 with pillared nanosheet morphology owing to its Brønsted acid site-rich property. The Al location in H-ZSM-5 and the corresponding acidic property are systematically investigated, and the theoretical simulations illustrate that the Al species at the intersection channels could lower the energy barrier of key aromatization step. The Al richly located at straight/sinusoidal would boost the isomerization reaction. Our work not only clarifies the structure-function relationship of acidic zeolite H-ZSM-5 in valuable chemicals synthesis from CO2 hydrogenation but also provides a novel protocol for controlled synthesis.