The present paper describes the successful synthesis of hierarchical ZSM-5 zeolite nanosurfaces with high porosity from the rice straw ash (RSA) by means of the hydrothermal method at varying time intervals in the presence of small amount of tetrapropylammonium bromide as a single template. The synthesized samples were characterized by X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), high resolution scanning electron microscopy (HR-SEM), and nitrogen adsorption–desorption analysis (BET). The XRD pattern confirms the formation of pure ZSM‐5 zeolite crystalline phase without any impurity phases. The IR spectrum shows a vibration band at 548 cm−1, which is assigned to the double 5-rings of MFI-type zeolites. The surface area results reveal the formation of additional mesoporosity without destroying the intensive microporosity in a hierarchical ZSM-5 zeolite, which is due to the addition of TPABr during the synthesis. The characterization results conclude that the long time process of hierarchical ZSM-5 zeolite nanosurfaces with high porosity have produced high crystallinity. © Springer International Publishing Switzerland 2017.