Li-7 nuclear magnetic resonance (n.m.r.) spectra obtained in static mode were used to characterize blends of polyamide-6 (PA6) and lithium sulfonated polystyrene ionomers (LiSPS) with 5.4 and 9.7 mol% sulfonate groups, for the blends with the higher degree of sulfonation a linear relation was found between full n.m.r. line width at half-maximum (FWHM) and the glass transition temperature (T-g, as determined by differential scanning calorimetry, d.s.c.). Magic angle spinning (MAS) spectra were also recorded and it was shown, in particular, that the line width of the central transition provides information on polymer miscibility on a scale smaller than 2 nm. Based on simulations of the Li-7 spectral data, it is suggested that three lithium species are present, whose concentration is determined by the sulfonated polystyrene/PA6 ratio in the blend; the miscibility of the blend is shown to be mainly correlated with one of the species.