Synthesis of α-oxygenated ketones from styrenes mediated by phenyliodonium diacetate in the presence of molecular oxygen and N-hydroxyphthalimide or N-hydroxybenzotriazole has been described. Addition of carbonyl oxygen at the α-position and formation of C-O bond at the β-position of styrenes was achieved under metal-free conditions. The present method is applicable for wide range of styrenes with a variety of functional groups.