A novel route has been reported for C-H hydroxylation of benzyl compounds directed by a 3,4,5-tribromopyrazole auxiliary via boronation/oxidation using BBr3 and NaBO3·4H2O. The strategy exhibits outstanding site selectivity and affords the corresponding phenols in moderate to excellent yields under metal-free conditions. Besides, this protocol can be achieved in one pot, which is highly promising as a practical method for use in a multistep organic synthetic process.