The asymmetric synthesis of chiral polycyclic ethers by an intramolecular [2+2] photocycloaddition is described. This process proceeded through a photocatalytically active iminium ion-based charge transfer (CT) complex under visible light irradiation. In this way a stereocontrolled [2+2] photocycloaddition is enabled leading to tricyclic products with good enantiomeric ratios.