A new kind of organosilane (1,6-bis(diethyl(3-trimethoxysilylpropyl)ammonium) hexane bromide) with a gemini-type structure was prepared and used as a mesoporogen for the synthesis of hierarchical porous ZSM-5 zeolite. There are two quaternary ammonium centers along with double-hydrolyzable -RSi(OMe)3 fragments in the organosilane, which results in a strong interaction between this mesoporogen and silica-alumina gel. The organosilane can be easily incorporated into the ZSM-5 zeolite structure during the crystallization process, and it was finally removed by calcination, leading to secondary pores in ZSM-5. The synthesized ZSM-5 has been systematically studied by XRD, nitrogen adsorption, SEM, TEM, TG, and solid-state one-dimensional (1D) and two-dimensional (2D) NMR, which reveal information on its detailed structure. It has a hierarchical porosity system, which combines the intrinsic micropores coming from the crystalline structure and irregular mesopores created by the organosilane template. Moreover, the mesoposity including pore size and volume within ZSM-5 can be systematically tuned by changing the organosilane/TEOS ratio, which confirms that this organosilane has high flexibility of use as a template for the synthesis of hierarchical porous zeolite.