High-performance and robust catalysts act as core drivers for catalytic ozonation to eliminate gaseous sulfur-containing volatile organic compounds (VOCs). Herein, nitrogen-doped carbon nanotubes embedded with Co species (Co@NCNT) are synthesized by thermolysis of a ZIF-67/melamine mixture. The carbon-confinement effects in Co@NCNT not only improve the stability of Co species but also regulate the electronic structure of Co�C bonds, consequently synergistically improving the catalytic ozonation performance. The experimental results indicate that the Co@NCNT catalyst could still remove ∼86% of odorous methyl mercaptan (CH 3 SH) after running for 60 h at 25 °C under an initial concentration of 50 ppm CH 3 SH and 40 ppm ozone, relative humidity of 60%, and space velocity of 600,000 mL h −1 g −1 , outdistancing reported values under comparable reaction conditions. Detailed characterization and theoretical simulations reveal that the electronic metal−support interaction of Co�C bonds in Co@NCNT significantly adjusts the electronic structure of Co species, thereby promoting ozone-specific adsorption/activation to convert the surface atomic oxygen (*O ad ) and •OH/ 1 O 2 /•O 2 − . Also, the electrons obtained from CH 3 SH in the electron-poor center transferred through the C�Co bond bridge to maintain the redox cycle of �Co 0/2+ → �Co 3+ → �Co 0/2+ and realize the efficient and stable removal of CH 3 SH into CO 2 /SO 4 2− /H 2 O. This work demonstrates that MOF-derived materials with tunable electronic structures achieve the stable removal efficiency for gaseous sulfurcontaining VOCs via electron transfer trade-offs and provide potential candidate catalysts for the application of air purification.