Atm. arsenic pollution, primarily caused by non-ferrous metal smelting and coal combustion, poses a significant environmental challenge.The removal of gaseous As2O3 from flue gas has become an urgent priority.Compared to synthetic adsorbents, natural manganese minerals (NMMs) possess advantages such as abundant reserves, low cost, and strong arsenic affinity, making them a promising candidate for large-scale gaseous As2O3 removal applications.This study investigates the As2O3 capture behavior of various NMMs through a combination of experiments and d. functional theory (DFT) calculationsPyrolusite (PY, 14.67 mg/g) and Hausmannite (HA, 20.69 mg/g) demonstrate superior adsorption performance compared to conventional adsorbents such as CaO (6.28 mg/g), Al2O3 (10.91 mg/g), and Fe2O3 (11.45 mg/g).DFT calculations and characterization results confirm that the adsorption of gaseous As2O3 by NMMs is primarily governed by chemisorption, with lattice oxygen serving as the key factor influencing the adsorption process.Surface oxygen sites on HA and PY serve as the primary active sites for As2O3 adsorption, where As2O3 forms stable covalent bonds with HA and PY.During the adsorption of gaseous As2O3, lattice oxygen is gradually consumed, while Mn facilitates the oxidation of arsenic.The findings of this study suggest that certain NMMs can efficiently capture gaseous As2O3 from high-temperature industrial flue gas, laying the foundation for the large-scale industrial application of adsorption-based As2O3 removal methods.