The highly enantioselective synthesis of a dibenzofuran-based C-2-symmetric chiral diol has been accomplished by the double enantioselective addition of diethylzinc to dibenzo[b,d]furan-4,6-dicarbaldehyde using a chiral 1,4-amino alcohol as a ligand. Among a series of chiral secondary diamines derived from the C-2-symmetric chiral diol, the chiral diamine with two pyrenyl groups can effectively separate enantiomeric H-1 NMR signals of various racemic acids.