Abstract: The ZSM-5@silicalite-1 core-shell zeolite catalyst was prepared by solid-phase synthesis method with ZSM-5 crystal as the core, and powders of silica (SiO₂), tetrapropylammonium bromide (TPABr) and ammonium fluoride (NH₄F) as raw materials. The structure of core-shell zeolite catalyst was characterized by means of X-ray energy spectrum analysis (EDS), transmission electron microscope (TEM), X-ray photoelectron spectroscopy analysis (XPS) and adsorption infrared spectrum of 2, 6-di-tert-butylpyridine (DTBPy-IR), and its catalytic performance on alkylation of toluene with methanol was investigated. The results showed that an all-silicon MFI zeolite (silicalite-1) shell formed on the outer surface of ZSM-5 core crystal by solid-phase synthesis method and that the core-shell catalyst showed high selectivity for p-xylene (PX). The effect of core size on the core-shell catalyst was also studied. It was found that the conversion of toluene decreased and PX selectivity increased as the core size increased. As a contrast, the core-shell zeolite catalyst was synthesized with traditional hydrothermal synthesis (liquid-phase synthesis method), and the effect of core crystal size was investigated. With the increase of core size, the toluene conversion over the core-shell zeolites synthesized by hydrothermal synthesis decreased first and then increased, while the PX selectivity was on the contrary. This study shows that the solid-phase synthesis method has better applicability for the shell coating of larger core crystals.