The development of methods for producing stereoregulated vinyl polymers has brought with it the necessity for the development of methods for determining the structure (i.e., stereochemical configuration) and conformation of their chains with the highest possible discrimination. Up to the present time, the polymer chemist has had x-ray fiber diagrams and empirical infrared absorption correlations’ at his disposal for this purpose. In this paper we describe a new method, based on the high resolution nuclear spin resonance (NSR) spectra of polymers in solution. This method has been employed only on polymers of methyl methacrylate but should have a broader applicability.