The pore-opening size of ZSM-5 zeolite was finely controlled by the chemical liquid deposition (CLD) method using SiCl4, TiCl4, and SbCl5 as a new type of deposition agents. After deposition the CLD zeolites were characterized by IR spectroscopy, XPS, NH3-TPD, and adsorption measurement. Their shape selectivity was compared in the sorption separation of meta- and para-isomers with different molecular diameters, such as m-xylene/p-xylene, m-dichlorobenzene/p-dichlorobenzene, and m-cresol/p-cresol. The ability of pore size controlling of different deposition agents depends on their reactivity with the zeolite surface hydroxyl groups and the readiness of migration of their oxides during calcination. SiCl4 is more efficient in pore size controlling than Si(OCH3)(4) and the other halides. The SiCl4-modified ZSM-5 zeolite samples exhibit excellent shape-selective separation properties for isomers of disubstituted benzene.