Limiting gaseous Hg0 emission is pressing due to the high toxicity in the ecosystem. Zeolites can be regarded as a promising alternative to carbon-based Hg0 adsorbents. However, the mass transfer limitations of conventional singe-sized zeolites constrain the industrial application of zeolites. This study explores the synthesis of hierarchical ZSM-5 zeolites using rice husk ash (RHA) and coal-fired fly ash (FA) as sustainable sources of silicon and aluminum, aimed at enhancing Hg0 removal from industrial flue gases. By adopting a one-step hydrothermal method, we introduced hierarchical porosity into the ZSM-5 framework, enhancing mass transfer and adsorption efficiencies. Iron (III) chloride (FeCl3) was utilized as an active species for modifying the hierarchical ZSM-5, significantly boosting its Hg0 adsorption capabilities. Fe/6RF-hZ demonstrating more than 92% mercury removal efficiency in 60 min under mixed flue gas condition. The structural and chemical attributes of the synthesized ZSM-5 were detailedly characterized, revealing notable differences in surface chemistry and porosity that correlate with varying calcination temperatures of RHA. TEA analysis reveals that hierarchical ZSM-5 zeolites outperform traditional sorbents in demercuration (DeHg) applications, with exceptional DeHg efficiency, energy efficiency (12 kWh), synthesis cost (860 $/ton), and carbon content (non-carbon). This study not only sheds light on the upcycling of solid wastes in synthesizing novel adsorbents but also contributes to the broader application of zeolitic materials in environmental remediation.