In this study, we present an efficient site-selective O-arylation method applicable to a broad range of complex arenes involving intramolecular aryl rearrangement. The reaction was facilitated by diaryliodonium salts bearing vicinal trifluoromethanesulfonate (OTf) groups. The procedure was initiated with selective C-H bond activation of arenes, which were then converted into diaryl ethers through nucleophilic aromatic substitution (SNAr). This synthetic method successfully affords complex diaryl ether derivatives, showcasing its practicality for the diversification of functionalized arenes and pharmaceutical agents.