Fluorinated phenols and other electron-deficient phenolic substrates are efficiently and cleanly iodinated by an iodine/iodide mixture employing alkaline conditions. This protocol turned out to be the most practical for the generation of such highly fluorinated iodophenols. For later application in coupling processes the protection of the phenolic hydroxymoiety is often required. Therefore, a practical iodination and subsequent methylation sequence was elaborated providing the highly fluorinated anisoles with good to excellent yields. The developed method is applicable for a broad scope of fluorinated phenols and analogues.