Aryl trifluoromethyl ethers (ArOCF3) are prevalent in pharmaceuticals, agrochemicals, and materials. However, methods for the general and efficient synthesis of these compounds are extremely underdeveloped and limited. Herein, we describe a highly efficient and general procedure for the direct O‐trifluoromethylation of unprotected phenols through a silver‐mediated cross‐coupling reaction using CF3SiMe3 as the CF3 source and exogenous oxidants. This novel oxidative trifluoromethylation provides access to a wide range of aryl trifluoromethyl ethers from simple phenols. The mild process was also applied to the late‐stage trifluoromethylation of a medicinally relevant compound. Combining two nucleophiles: The direct oxidative O‐trifluoromethylation of phenols with CF3SiMe3 provides a general and practical method for the preparation of aryl trifluoromethyl ethers. A wide variety of functional groups are tolerated under these conditions, and the method can also be employed for the late‐stage trifluoromethylation of complex pharmaceutically relevant molecules (NFSI= N‐fluorobenzenesulfonimide).