Fluoroalkyl ethers have attracted considerable research interest in the fields of pharmaceutical, agrochemical, nuclear imaging and material sciences, forging the development of new synthetic methods to access this class of compounds. Radical fluoroalkoxylation has recently emerged as a promising approach for synthesizing fluoroalkyl ethers. Herein, a solid, easy-to-access redox-active N−O reagent, 1-(fluoromethoxy)-3-methyl-benzotriazolium triflate (FMBT), serving as a radical source of (mono)fluoromethoxy group under photocatalytic conditions, was introduced. The synthetic potential of FMBT was demonstrated in the functionalization of olefins to access amino and keto-monofluoromethyl ethers, benefiting the related study in the context of chemical biology and drug discovery. (Figure presented.).