A method to achieve rhodium(III)‐catalyzed, potassium acetate enabled intermolecular C–H amination of ketoximes using various benzenesulfonamide, especially 4‐nitrobenzenesulfonamide is reported. Various aryl ketoximes substituted with electron‐withdrawing functional groups were all well tolerated and produced the corresponding products in moderate to good yields. A preliminary mechanistic study revealed that potassium acetate is essential to realizing intermolecular amination.