Alkane catalytic cracking is regarded as one of the most significant processes for light olefin production; however, it suffers from serve catalyst deactivation due to coke formation. Herein, HZSM-5/MCM-41 composites with different Si/Al2 ratios were first prepared by the hydrothermal method. The physicochemical properties of the prepared catalysts were analyzed by a series of bulk and surface characterization methods, and the catalytic performance was tested in n-decane catalytic cracking. It was found that HZSM-5/MCM-41 showed a higher selectivity to light olefins and a lower deactivation rate compared with the parent HZSM-5 due to an enhanced diffusion rate and decreased acid density. Moreover, the structure-reactivity relationship revealed that conversion, light olefin selectivity, and the deactivation rate strongly depended on the total acid density. Furthermore, HZSM-5/MCM-41 was further extruded with γ-Al2O3 to obtain the catalyst pellet, which showed an even higher selectivity to light olefins (∼48%) resulting from the synergy effect of the fast diffusion rate and passivation of external acid density.