We report the use of band-selective 2D HSQC NMR spectroscopy to rapidly determine the stereoregularity of polymers usually analyzed by 1D 13C NMR spectroscopy. This approach reduced the time required to characterize the triad stereosequences of polyacrylonitrile from about an hour to a few minutes, and can be performed with sufficient 13C resolution to resolve higher-order stereosequences, such as the pentads of polypropylene.