Nitrous oxide (N 2 O), recognized as a significant greenhouse gas, has received insufficient research attention in the past. In view of their low energy consumption and cost-effectiveness, the application of porous materials in adsorption is increasingly regarded as a potent strategy to reduce N 2 O pollution. In this study, a series of microporous porous carbons with a preeminent specific surface area (244.54−2018.08 m 2 g −1 ), which are derived from the fast-growing eucalyptus bark, were synthesized by KOH activation at high temperatures. The obtained materials demonstrated a relatively fine N 2 O capture capability (0.19− 0.68 mmol g −1 ) at normal temperature and pressure. More importantly, the optimal pore size affecting N 2 O adsorption (0.8 and 1.0 nm) has been detected, which is a meaningful view that has never been put forward in previous studies. The rationality of the N 2 O adsorption mechanism was also validated by combining the experimental analysis and Grand Canonical Monte Carlo (GCMC) simulation. The calculated results showed that 0.8 and 1.0 nm of the porous carbon were the preferred pore sizes for N 2 O adsorption, and the interaction force between N 2 O and the pore wall decreased with the increase of distance. This study provides a significant theoretical basis for the preparation of biomass porous carbon with excellent N 2 O adsorption performance and practical adsorption application.