A facile and metal-free method for the direct C(sp3)-H bond alkoxylation of 3-methylfuranocoumarins with alcohols has been disclosed. Selectfluor enabled the (hetero)benzylic C-H etherification by tuning the reaction temperature and solvent. Various alcohols were compatible in this transformation with suitable yields. The mechanistic studies revealed that the reaction might undergo the double addition process of alcohols, as well as the departure of a fluoride anion and the formation of an oxonium ion.