High-resolution C-13 and H-1 NMR measurements were carried out to determine the tacticity of poly(n-butyl methacrylate) with particular focus on the peak assignments for the n-alkyl side chain. Both free radical and anionic poly(n-butyl methacrylate) were examined, with the former being predominantly syndiotactic and the latter isotactic. The H-1 NMR resonances for the n-alkyl chain of these polyacrylics show a combination of effects from configurational sensitivity and homonuclear scaler interactions. A combination of J-resolved H-1 NMR and H-1-C-13 heteronuclear correlated 2D NMR spectra was used to characterize the previously unobserved, long-range chemical shift effects due to tacticity.