Aiming to prepare industrial material of ZSM-5 zeolites with strong hydrophobicity, stable performance and adaptability to varied working conditions for adsorption and purification of volatile organic compounds (VOCs), high-silica ZSM-5 zeolites with different morphologies were synthesized by adding ammonium acetate in a hydrothermal system, using ZSM-5 zeolites with silicon to aluminum ratio of 300 as the seed crystal. The influence of ammonium acetate addition on morphologies and hydrophobicity of high-silica ZSM-5 zeolites were investigated by XRD, SEM, XRF, N2 adsorption-desorption and water contact angle characterization methods. The influence of morphologies on hydrophobicity and toluene adsorption performance of ZSM-5 zeolites were investigated on static and dynamic adsorption experimental device. The results show that high-silica ZSM-5 zeolites with coffin-shaped, hexagonal-plate and rod-shaped morphology can be obtained by adjusting the amount of substance ratio of ammonium acetate to be 0, 0.05 and 0.1 times of SiO2, respectively. Among them, the high-silica ZSM-5 zeolites with rod-shaped morphology (ZSM-5-0.1) had the strongest hydrophobicity with a hydrophobic index of 8.36 and a water contact angle of 35.05°. The water vapor and toluene adsorption of ZSM-5-0.1 were least affected by humidity: under relative humidity of 50%, 80% and 100%, the dynamic saturated adsorption capacity of water vapor is 0.66%, 0.92% and 1.15%, respectively; in addition, Under the humidity of 80%, the GHSV of 10000h-1, the breakthrough adsorption capacity of ZSM-5-0.1 for toluene at mass concentration of 4000 and 2000mg/m3 is basically equivalent with values of 0.053 and 0.051g/g, respectively, and the diffusion rate of toluene in ZSM-5-0.1 was least affected by water vapor, and its diffusion rate constants were 0.145 and 0.133 min-1, respectively, which were consistent with the Y-N model.