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Hollow zeolites are normally made by synthesizing parent rigid zeolites form soluble silica-alumina suspension followed by removal of the aluminum-deficient centers, during which the uniformity of hollow zeolites is compromised. Herein, two uniform spherical hollow ZSM-5 (hZSM5) with distinct morphologies, monodispersed (mhZSM5) and networked (nhZSM5), were hydrothermally synthesized using premade Stöber SiO₂ spheres along with structure directing agents with and without aluminum. Subsequently, both mhZSM5 and nhZSM5 supports were impregnated with mono- and multimetallic Cu-based catalysts to investigate CO₂ hydrogenation with in-depth catalyst characterizations (HRTEM-EDX, Pyridine-FTIR, H₂-TPR, XPS, XANES, and DRIFTS). It was evidenced that uniform and decent morphology of mhZSM5 spheres arises from the existence of framework-intrinsic Al³⁺. Besides, it was revealed that …