Zeolite–zeolite composite composed of alumina-rich hierarchically porous ZSM-5 cores and high-silicon MFI shells was prepared by a hydrothermal synthesis procedure, in which a commercial ZSM-5 zeolite with a SiO2/Al2O3 of 36 was treated by an alkaline solution and then used as a supporter for epitaxial growth of a polycrystalline Silicalite-1 zeolite shell (denoted as MMZsa). Acid sites associated with framework Al on exterior surfaces of ZSM-5 zeolite cores are therefore passivated in different degrees by the epitaxial MFI zeolite shell. The structural, crystalline, and textural properties of the as-synthesized samples were characterized by x-ray powder diffraction (XRD), energy-dispersive x-ray spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), N2 adsorption-desorption, in situ IR spectra of pyridine and NH3-TPD. Aluminum species were observed to transfer from the alumina-rich cores to the high-silica shells. The adjustable thickness and SiO2/Al2O3 ratio of the shell offer the as-synthesized composite a potential and high-efficiency catalyst for methanol conversion into gasoline and diesel. As compared with the commercial ZSM-5 zeolite, the composite catalyst exhibits excellent catalytic performances with a longer catalytic life as well as a higher conversion and a slightly higher yield of diesel oil.