AbstractThe paper recalls some aspects of the fascinating history of the discovery by Giulio Natta and his coworkers of the stereospecific polymerization of α‐olefins and of the determination of the structure of synthetic stereoregular polymers.The most relevant recent advances in the comprehension of the mechanisms regulating their synthesis with heterogeneous supported catalysts and with the newly discovered homogeneous metallocene‐based catalysts are briefly outl