A one-pot stepwise Ce(III)/photoassisted cross-dehydrogenative coupling/fluorooxidation process was developed to construct C3-heteroaryl 3-fluorooxindoles in high efficiency. This protocol was conducted under mild conditions using readily available chemical feedstocks in the absence of precious metals, oxidants, and additives, affording corresponding products in moderate-to-good yields through recrystallization with favorable functional group compatibility. In addition, our methodology demonstrates a successful strategy involving the simultaneous establishment of C–C, CO, and C–F bonds with simple operation and innovative direct transformation of CC bonds to functionalized C–C bonds.