Improving the stability of sensitive catalytic systems is an emerging research topic in the catalysis field. However, the current design of heterogeneous catalysts mainly improves their catalytic performance. This paper presents a single-atom catalyst (SAC) strategy to improve the cobalt-catalysed fluorination of acyl chlorides. A stable CoÀ F intermediate can be formed through the oxidative fluorination of Co 1 À N 4 @NC SAC, which can replace the unstable highvalent cobalt catalytic system and avoid the use of phosphine ligands. In the SAC system, KF can be employed as a fluorinating reagent to replace the AgF, which can be applied to various substrates and scale-up conversion with high turnover numbers (TON = 1.58 × 10 6 ). This work also shows that inorganic SACs have tremendous potential for organofluorine chemistry, and it provides a good reference for follow-up studies on the structure-activity relationship between catalyst design and chemical reaction mechanisms.

CH bond activation has always been attractive research in that it brings the most rapid and atom‐economic transformation approach to synthesize and further utilize the existing chemicals. As what has been published, due to its special and unique structural and electronic properties, rare‐earth metal complexes have been used as the efficient catalyst for CH functionalization in organic synthesis, electrocatalysis, and photocatalysis. This article describes a few examples of the high‐efficiency rare‐earth metal catalysts and the CH functionalization by rare‐earth metal catalysis in organic synthesis.