China′s energy structure will likely remain dominated by coal combustion for a period of time. Titanium silicalite zeolites (TS-1) with MFI topology were adopted for adsorption and reduction of VOCs in coal-fired flue gas treatment in this work. We treated the zeolites with alkali solutions (NaOH, NH_4OH, TPAOH ) of different strength and properties to construct a differentiated hierarchical pore structure. The relative content of Si—OH groups (including isolated Si—OH groups on the outer surface and hydroxyl nests at internal defect sites) was also regulated in order to improve VOCs hydrophobic adsorption capacity. The changes of zeolitic framework structure, internal defects and other relevant properties were investigated using XRD, BET, UV-vis, IR, SEM and TEM. The results showed that the NaOH solution treatment significantly etched the framework, leading to a decreasein ordered pores and increase in defects, which resulted in a sharp decrease in adsorption capacity. NH_4OH solution could dredge the pores and remove amorphous silicon species, improving the adsorption performance of VOCs, but the hydrophobic ability decreases slightly. The dissolution-recrystallization effect in TPAOH treatment process led to the formation of numerous ordered zeolitic frameworks. The development of micropores was significantly improved, and the internal defects were repaired, resulting in a significant improvement of hydrophobic adsorption performance of VOCs. The adsorption capacity of VOCs was increased by 50%, and the static water adsorption capacity was reducedby 18%.