Selective functionalization of a single sp3 C-F bond of the CF3 group represents an appealing way to generate the pharmaceutically privileged difluoromethylene moiety. Herein, a novel protocol for the C-F bond etherification of trifluoromethylalkenes and phenols is reported. A variety of alkenyl difluoroaryloxy ethers are obtained with good chemoselectivity and functional group tolerance. DFT calculation results and control experiments suggest that metal ion Cs+ might be involved in this defluorooxylation. Furthermore, the desired product exhibits a good insecticidal activity.