Wen Jiang, Yuxuan Wu, Kecan Dou, Qiang Xiao, Fumin Zhang, De‐Li Chen, Weidong Zhu
ABSTRACT The transition from conventional single‐atom catalysts to heteronuclear neighboring single‐atom catalysts presents a compelling strategy to address the limitations associated with isolated metal sites in multielectron oxidative transformations. Herein, we report a Co–Mn heteronuclear single‑atom catalyst (Co 1 ‐Mn 1 /NC) in which atomically dispersed Co and Mn species are anchored on a nitrogen‑doped carbon support to form well‑defined neighboring active pairs with an interatomic distance of ∼2.6 Å. This configuration provides a synergistic platform that markedly outperforms its monometallic Co and Mn counterparts in two challenging oxidative C–H functionalization reactions: the selective oxidation of acenaphthene to 1‑acenaphthenol (99.9% conversion, 97.7% selectivity) and the oxidative condensation of benzyl alcohol with methanol to benzaldehyde dimethyl acetal (63.4% conversion, 94.7% selectivity). Atomic‑resolution characterization and DFT calculations elucidate the origin of this synergy, revealing a division of labor between the two metal centers. In acenaphthene oxidation, the Co–Mn pair cooperatively activates molecular oxygen and facilitates C–H bond dissociation with a substantially reduced energy barrier. In the oxidative condensation, the Co site preferentially activates methanol while the adjacent Mn site stabilizes the key *PhCHO intermediate. This work establishes heteronuclear neighboring Co–Mn pairs as a platform for synergistic multifunctional catalysis.