Rational design and fabrication of hierarchical zeolites with desired structures has long been of essential and practical interest to engineers and scientists. Featuring a hierarchical nano-shell and enclosed interior space, hollow nano ZSM-5 crystals exhibit excellent capability as the key catalyst in various important reactions. However, it has been an ever-increasing but challenging task to directly fabricate hierarchical hollow Al-rich nano ZSM-5 crystals since only limited mesoporosity in ZSM-5 zeolites with Si/Al < 15 can be generated by desilication. Here, a one-step Al-distribution regulated desilication approach combining the synthesis of an Al-rich parent ZSM-5 (Si/Al = 12.5) with locally concentrated Al (LCA) domains and a simple alkali-treatment step is presented. The existence of LCA domains and their impacts on the selective desilication process were validated by diffuse reflectance UV spectroscopy and filtrate analysis, and approximately 49% of Al atoms emerged in Z5-LCA samples as Al species in close contact. Compared with its parent zeolite, the hierarchical hollow nano ZSM-5 crystal exhibited increased catalytic activities as well as ∼2-fold improved selectivities for high-value light olefins (C₂H₄ and C₃H₆) in the catalytic cracking of decalin (a model bulky naphthene molecule) and a real naphtha feedstock. These findings expand our knowledge on achieving desirable zeolite structures by regulating framework Al distribution, and suggest a promising new catalyst toward highly selective production of light olefins from naphthene feedstocks.