Inspired by the alveolar configuration, an alveoli-like ZSM-5 and the corresponding platinum encapsulated nanocomposite (Pt@PZ5) were fabricated via a dual-template method and a controlled selective desilication-recrystallization strategy. The dimensions of the central cavity, interconnected zeolitic vesicles, and mesoporous shell could be tuned by adjusting the synthesis parameters, as verified by scanning electron microscopy, transmission electron microscopy, nitrogen physisorption investigations, X-ray photoelectron spectroscopy, and X-ray diffraction techniques. Thanks to these properties and merits, the alveoli-like Pt@PZ5 showed the highest catalytic performance with excellent stability, obtaining 100% benzene conversion at 180 °C. Adsorption experiments combined with a finite-element simulation study uncovered that the alveolar architecture could expedite the accumulation of reactants and boost mass transfer; the conversion of intermediates in the voids could be further facilitated, giving optimal catalytic performance. Additionally, the alveolar architecture is resistant to metal sintering (5-20 nm) and leaching, even after calcination at 850 °C for 360 min. This work provides an alveolar concept into the rational design of efficient catalysts for fundamental catalytic action.