AbstractIn the last few years several non‐metallocene catalysts have been disclosed as efficient catalysts for the stereospecific polymerization of propene.In this paper we summarize some recent literature data and some new results concerning the stereochemical mechanism of propene polymerization promoted by late transition metal systems and group 4 metal bis(phenoxyimine) systems. NMR analysis of the fine structure of the polymers obtained, in some cases using isotopically enriched reagents, provides valuable information on the regiochemistry and stereochemistry of the polymerization.