The invention relates to a method for preparing a series of novel phosphinimine ruthenium carbine complexes with high thermal stability and application of the novel phosphinimine ruthenium carbine complexes to the metathesis reaction of olefin, and mainly overcomes the disadvantages that the asymmetric transformation exists and the reaction still cannot be effectively realized at high temperature in the metathesis reaction for forming tetrasubstituted olefin under the catalysis of a ruthenium carbine complex, the ruthenium carbine complex is not applicable to basic functional groups (such as NH2- and CN-) and the initiation rate and increment rate are low in the previous literature. The problems can be well solved by adopting the technical scheme of metal ruthenium carbine complex ligands which have a general formula of Ru(=CHAr)Cl2L(R<1>P=NR<2>) and the synthesis thereof, wherein Ar is (C6-C14) aryl; L is an uncharged electron donor, namely a phosphino or aza five-membered ring carbine ligand; R1 is phenyl, cyclohexyl, tert-butyl, ortho-pyridyldiphenyl, and ortho-furyldiphenyl; and R2 is aryl, pyridyl and picolyl.