A chiral spiro phosphine-nitrogen-sulfur tridentate ligand having the structure of Formula I or Formula II, their racemates, optical isomers or their catalytically acceptable salt thereof, wherein, R 1 is selected from C 1 -C 10 alkyl, phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl, heteroaryl or benzyl, and the substituent on said phenyl is C 1 -C 10 alkyl or alkoxyl, with a substituent amount ranging from 1∼5, and said heteroaryl is furyl, thienyl or pyridyl; R 2, R 3, R 4 and R 5 are independently selected from H, C 1 - C10 alkyl, phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl, heteroaryl or benzyl, and the substituent on said phenyl is C 1 -C 10 alkyl or alkoxyl, with a substituent amount of 1∼5, and said heteroaryl is furyl, thienyl or pyridyl; C 1 -C 10 alkoxyl; or R 2 ∼R 3, R 4 ∼R 5 are incorporated into C 3 -C 7 aliphatic ring, aromatic ring; R 2, R 3, R 4 and R 5 can be the same or different; R 6, R 7 are independently selected from H, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, Ci-Cio alphatic amido group, and n=0∼3; or when n≥2, two adjacent R 6 groups or two adjacent R 7 groups can be incorporated into a C 3 -C 7 aliphatic ring or aromatic ring and R 6 and R 7 can be the same or different; R 8, R 9 are independently selected from Ci-Cio alkyl, Ci-Cio alkoxy, phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl, heteroaryl or benzyl, and the substituent on said phenyl is C 1 -C 10 alkyl or alkoxyl, with a substituent amount of 1∼5,and said heteroaryl is furyl, thienyl or pyridyl; or R 8 and R 9 groups can be incorporated into a ring by C 2 -C 4 carbon chain, carbon chain containing N, O, or S, aromatic nucleus or heterocyclic aromatic ring; R 8, R 9 can be the same or different. wherein, R 1 is selected from C 1 -C 10 alkyl, phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl, heteroaryl or benzyl, and the substituent on said phenyl is C 1 -C 10 alkyl or alkoxyl, with a substituent amount ranging from 1∼5, and said heteroaryl is furyl, thienyl or pyridyl; R 2, R 3, R 4 and R 5 are independently selected from H, C 1 - C10 alkyl, phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl, heteroaryl or benzyl, and the substituent on said phenyl is C 1 -C 10 alkyl or alkoxyl, with a substituent amount of 1∼5, and said heteroaryl is furyl, thienyl or pyridyl; C 1 -C 10 alkoxyl; or R 2 ∼R 3, R 4 ∼R 5 are incorporated into C 3 -C 7 aliphatic ring, aromatic ring; R 2, R 3, R 4 and R 5 can be the same or different; R 6, R 7 are independently selected from H, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, Ci-Cio alphatic amido group, and n=0∼3; or when n≥2, two adjacent R 6 groups or two adjacent R 7 groups can be incorporated into a C 3 -C 7 aliphatic ring or aromatic ring and R 6 and R 7 can be the same or different; R 8, R 9 are independently selected from Ci-Cio alkyl, Ci-Cio alkoxy, phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl, heteroaryl or benzyl, and the substituent on said phenyl is C 1 -C 10 alkyl or alkoxyl, with a substituent amount of 1∼5,and said heteroaryl is furyl, thienyl or pyridyl; or R 8 and R 9 groups can be incorporated into a ring by C 2 -C 4 carbon chain, carbon chain containing N, O, or S, aromatic nucleus or heterocyclic aromatic ring; R 8, R 9 can be the same or different.