The excessive CO2 emission has gained global attentions due to its potential effects on climate change, plant nutrition deterioration, and human health and safety. Metal-organic frameworks (MOFs) featured with high specific surface area, adjustable pore size, and tailorable morphology have been widely applied for CO2 capture. However, some drawbacks of poor mechanical stability and uneven distribution of mesopores limit their further applications. Herein, we demonstrate a one-step synthesis of bimetallic center framework (OSSBCF) and pore reconstruction (PRC) strategy to prepare the hierarchical porous Zn/Co-ZIF@ANF aerogels. This unique design achieves the construction of efficient gas transfer channels and creates massive micropores with abundant Lewis basic adsorption sites. Benefiting from theses merits, the bimetallic Zn/Co-ZIF@ANF aerogels demonstrate high MOFs loading mass of 47.51 wt%, high specific surface area of 686.39 m2g−1, and large porosity of 99.31 %. Moreover, the bimetallic Zn/Co-ZIF@ANF aerogels exhibit an enhanced CO2 adsorption capacity of 5.99 mmol/g and CO2/N2 adsorption selectivity of 35 at 25 °C and 1 bar. The CO2 capacity of bimetallic Zn/Co-ZIF@ANF aerogels keep up to 95.19 % after ten cycles of CO2 adsorption, indicating the excellent long-term recycle stability. Therefore, this study provides a promising strategy to engineer hierarchical porous bimetallic MOF aerogels toward practical CO2 capture.