The first visible-light-induced acyl radical Smiles rearrangement to transform biaryl ethers to hydroxybenzophenones under mild and metal-free conditions is reported. Using the dual catalysis of hypervalent iodine(III) reagents and organophotocatalysts, ketoacids readily generate acyl radicals and undergo 1,5- ipso addition. This method can construct electron-deficient and electron-rich hydroxybenzophenones with excellent chemoselectivity and on gram scale. The performance of the reaction in neutral aqueous conditions holds potential for future biomolecule applications.