Acid-catalyzed Friedel–Crafts alkylation of 1,3-dicarbonyl compounds with electrophilic alcohols, is known to be an effective CC bond forming reaction. However, until now, this reaction has not been amenable for -alkylation of aryl methyl ketones because of the notoriously low nucleophilicities of these compounds. Therefore, -alkylation of aryl methyl ketone relies on precious metal catalysts and also, the use of primary alcohols is mandatory. In this study, we found that a system composed of a Fe(OTf)₃ catalyst and chlorobenzene solvent is sufficient to promote the title Friedel–Crafts reaction by using benzhydrols as electrophiles. 3,4-Dihydro-9-(2-hydroxy-4,4-dimethyl-6-oxo-1-cyclohexen-1-yl)-3,3-dimethyl-xanthen-1(2 H)-one was also applicable as an electrophile in this type of benzylation reaction. On the basis of this result, a three-component reaction of salicylaldehyde, dimedone, and aryl methyl ketone was also developed, and this provided an efficient way for the synthesis of densely substituted 4H-chromene derivatives.