Although stereochemistry plays a key role in the structure and function of biological polymers it was not until the discovery of isotactic polypropylene, now about 60 years ago, that the role of stereochemistry was seen to be of importance in synthetic polymers. Staudinger had predicted that although the nature of the bonding in small molecules and in macromolecules was identical, polymers would have special properties associated with the size of macromolecules. This article outlines how stereochemical studies demonstrate Staudinger's prescience in many ways. The story takes us from the tactic nature of vinyl polymers and their unrecognized and recognized chirality, to helicity, a characteristic shared by biological and certain synthetic polymers. There is an advantage to studying stereochemistry in synthetic polymers: their chiral characteristics can be manipulated in ways not possible in biological polymers, allowing discovery of new phenomena that cross boundaries outside of the polymer realm.