The microstructural analysis of poly(alpha-tocopherylmethacrylate) (PMVE) was carried out by one-dimensional C-13 n.m.r. spectroscopy. The sensitivity of both aromatic and methyl (those attached to the aromatic ring) carbon signals to the stereosequences depends mainly on the proximity of these carbons to the maximum shielding zone of the neighbouring conjugated blocks formed by the aromatic ring and the pyran cycle. The sensitivity of the ester carbonyl signal to the chain microstructure is influenced mainly by the gamma-gauche shielding effect. For PMVE prepared by radical polymerization Bernoullian statistics account satisfactorily for the observed relative intensities at the tried and pentad level.