Ethane (C₂H₆) is an important inexpensive and widely available fuel resource. High-value use of C₂H₆ has become increasingly important. Catalytic dehydrogenation of C₂H₆ to ethylene (C₂H₄) has attracted much attention in recent years due to its high energy efficiency. The direct non-oxidative ethane dehydrogenation (EDH) to ethylene is a promising strategy to produce ethylene and hydrogen at the same time. In this research, Cr/HZSM-5 catalyst with superior stability was synthesized and exhibited an C₂H₆ converting activity of 1.47 μmol/(g·s) with the corresponding C₂H₆ conversion and C₂H₄ selectivity of 37.3% and 90%, respectively. The synergistic effects of Si and Al in supporting materials were investigated by comparing Cr/HZSM-5 with SBA-15, SiO₂ and Al₂O₃ supported ones, which contains either Al or Si with different structures. Characterization results indicated that the intimate interactions between Cr and support significantly improved the catalytic performance. The presence of Al in the support promoted the formation of more active Cr⁶⁺ species by forming the aluminum‑chromium-chromate (Cr-O-Al) structures which were more efficient to active C-H bond and form (Cr, Al)-OH groups during the reaction. Meanwhile, the formation of internal silanol group with the dissociative adsorbed H* could stabilized the active Cr phase to achieve a stable dehydrogenation activity.