Constructing zeolite catalysts with excellent mass transfer and active site accessibility is the key to improving their catalytic efficiencies. Herein, a zeolite subcrystal catalyst with high short-range ordering but X-ray amorphism is prepared to minimize the existing molecular mass-transfer barrier of conventional zeolite catalysts. Various characterizations confirm its size of smaller than 10 nm, definite MFI framework, complete opened micropore channel, and abundant accessible acid sites. Moreover, physical and chemisorption results reveal that the high short-range ordering MFI zeolite subcrystal possesses negligible intracrystalline diffuse limitation and utmost accessibility for the active site. As anticipated, the zeolite subcrystal catalyst not only demonstrates high cracking efficiency in polyolefin cracking reactions but also exhibits outstanding catalytic activity and resistance to carbon deposition in macromolecular furfuryl alcohol etherification reaction. The controlled MFI zeolite subcrystal catalyst synthesis strategy is expected to extend to a variety of microporous materials.