Modified C-13 NMR assignments of the aromatic C-2 carbon of poly(2-vinylpyridine) in methanol-d(4) are proposed on the basis of compliance with the necessary statistical relations between pentad sequence intensities. The spectral analysis shows that the C-2 resonance assignments are more complex than previously believed. The relative ordering of the mmrm and mmrr pentad resonances is opposite to previous assignments. Significant overlap between the rmmr and mmrr pentads is found, indicating that the separation of the isotactic and heterotactic triads is not clean. The three syndiotactic pentad resonances could be reliably identified.