SUMMARY: Copolymers of styrene and ethyl acrylate are prepared by radical polymerization and analysed with respect to microstructure by means of nuclear magnetic resonance. Using 13 C NMR, the compositional styrene-and ethyl acrylate-centered triads can be determined and compared to theoretical values. Good agreement between experimental and calculated triad concentrations are obtained for styrene-rich copolymers. Ethyl acrylate-rich copolymers exhibit significant deviations from the calculated values in particular for the ethyl acrylate homotriads. Using on-line coupled SEC-1 H NMR, the chemical composition across the molar mass axis can be monitored. It is found that ethyl acrylate-rich copolymers exhibit a broader molar mass and chemical composition distribution than styrene-rich copolymers. The results indicate that the block character of the copolymers with respect to ethyl acrylate units increases with increasing molar mass.