The physical properties and chemical compositions of porous carbons are crucial factors in determining their effectiveness in adsorbing CO2. Cellulose-based porous carbon has emerged as an outstanding candidate adsorbent for CO2 capture. The research involved the creation of hierarchically nitrogen-doped porous carbon (HNC) using a 3D cellulose alcogel (CA) as substrate, which was prepared through a thermal introduced phase separation (TIPS) method combined with hydrolysis treatment. The plentiful functional groups of CA offered abundant growth sites for the introduction of ZIF-8 crystals. CA/ZIF-8 composite alcogel (CZA) with greater surface area and superior thermal stability compared to CA was successfully fabricated and used as precursor for the production of HNC. The important effects of microporosity and surface chemistry of HNC samples on CO2 capture were discussed in-depth. HNC-350–850 displayed a hierarchically porous structure with a large number of micropores and abundant N/O/Zn-doped functional groups, exhibiting high CO2 uptakes at 1 bar (3.56 mmol/g at 25 °C), good IAST CO2/N2 (15/85, V/V) selectivity of 16.31 at 25 °C, and outstanding regenerability with ∼100 % CO2 adsorption capacity retained after ten cycles. In the two-component CO2/N2 (15/85, V/V) competitive adsorption process, the maximum breakthrough periods for CO2 (433.1 s) is significantly longer than that of N2 (3.8 s). The CO2 breakthrough adsorption capacity reached 1.79 mmol/g at 25 °C and 1 bar with the separation coefficient of 45.8 for CO2 over N2. These results confirmed that HNC, in addition to having excellent CO2/N2 selectivity, demonstrated good feasibility for practical use. The green and practicable synthetic route described in this study is not only expected to offer novel adsorbents for high performance CO2 capture, but also provide a new theoretical foundation for the development of cellulose-based porous materials.