A hydroxy group-directed Paternò-Büchi (PB) reaction between arylglyoxylates and furfuryl alcohols afforded the corresponding oxetanes regio- and diastereoselectively. Furthermore, the PB reaction between β-naphthylglyoxylate possessing diisopropyl (R,R)-tartrate moiety and furfuryl alcohol achieved high chiral induction to produce the corresponding optically pure oxetane after the removal of the chiral auxiliary.