The invention relates to an alkene polymerization catalyst with thienyl substituting silane. The catalyst comprises a solid titanium catalyst component whose main components are titanium, magnesium and halogen, an aluminum alkyl compound component, and an organo-siloxane component containing two thienyl substituents, wherein the organo-siloxane component containing two thienyl substituents is represented by the general formula (I), and the molar ratio of titanium: aluminum: silicon in each component of the catalyst is 1:50-150:5-50. When the catalyst of the invention is used in propylene polymerization, polymerization products with very high isotacticity can be obtained, and the yield is relatively high.