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Graphical abstract Highlights • Hierarchical Hβ zeolite was synthesized by a modified steam-assisted conversion. • Optimized hierarchical Hβ shows outstanding catalytic performance in alkenylation. • Various techniques were employed to reveal the origin of the excellent catalytic properties. • Spent hierarchical Hβ zeolite catalyst can be easily recovered via a facile calcination. • The developed hierarchical Hβ zeolite can be a practical catalyst for alkenylation. Abstract In this work, using phenylacetylene as alkenylating agent, the alkenylation of p- xylene on a series of hierarchical Hβ (Hier-Hβ) zeolites prepared by a modified steam-assisted conversion (SAC) method under different preparation conditions was firstly investigated. Various characterization techniques including X-ray diffraction (XRD), X-ray fluorescence (XRF), argon adsorption-desorption, ammonia temperature-programmed desorption (NH 3 -TPD), pyridine-IR (Py-IR), and thermogravimetric Analysis (TGA) were adopted to discover the relationship of structure-performance in alkenylation. The results demonstrate that the optimized Hier-Hβ zeolite exhibits an outstanding alkenylation catalytic performance, which is much better than the traditional microporous Hβ zeolite. It can be found that the alkenylation catalytic properties of the as-prepared Hier-Hβ zeolites are dramatically affected by their properties of acidic sites and textural properties, which are significantly dependent on the preparation process parameters for SAC process. Moreover, the spent Hier-Hβ zeolite catalyst can be completely refreshed by a simple calcination method. In a word, the optimized Hier-Hβ catalyst prepared by a modified SAC approach demonstrates great potential to promote alkenylation of aromatics with alkynes to their corresponding alkylaromatics. [ABSTRACT FROM AUTHOR]