Highly crystalline nano-MFI-type zeolites containing different elements were synthesized, and the sorption effects of the elements on volatile organic compounds (VOCs) were investigated. The results showed that the optimal toluene and acetone breakthrough time of the synthesized zeolites was 2.1 and 1.9 times as long as that of the commercial zeolite, respectively. For a weakly polar toluene molecule, MFI zeolites (aluminum-free) showed better adsorption properties than aluminum-containing zeolites. For the highly polar acetone molecule, zeolites with a Si/Al ratio of 87 showed the highest adsorption capacity, which was 7% higher than that of the all-silica zeolite and 1.4 times that of the commercial zeolite. Furthermore, MFI zeolites with Ti replacing part of Al proved to have better performance for highly polar molecules. In the adsorption process of VOCs, in addition to internal diffusion, diffusion on the external surface of the zeolite also played a remarkable role, and the adsorption data of all samples fitted better with the pseudo-first-order model. This study may provide a reliable structure-performance relationship for the synthesis of nanosized zeolite-based adsorbents and their use in the industrial recovery/treatment of VOCs.