The invention discloses an axially chiral cyclo-diphenol compound as well as a preparation method and application thereof. The structural formula of the axially chiral cyclo-diphenol compound is shown in the formula I or formula II, wherein n represents a natural number of 1-5, R1 and R2 represent at least one substituent group on a benzene ring, R3 represents at least one substituent group on a ring A, and R1, R2 and R3 are respectively and independently selected from C1-C5 alkyl, aryl, halogen, nitryl, ether group, sulphonyl, phosphonyl, amino, amide group and ester group; and aryl can be phenyl. The axially chiral cyclo-diphenol compound shown in the formula I or formula II can be used as a chiral ligand in asymmetric reaction. The axially chiral cyclo-diphenol compound shown in the formula I or formula II can be successfully applied to asymmetric reaction of aryl formaldehyde and diethylzinc and has relatively high reaction activity and enantioselectivity.