NMR spectroscopy has been coupled on-line to capillary isotachophoresis (cITP) to enhance structural analyses of dilute charged species through separation and sample concentration. Microcoils, the most mass-sensitive NMR probes available, provide optimal detection for cITP/NMR. To evaluate the utility of cITP/NMR for natural product analysis, a homogenate of the hypobranchial gland from the marine snail Calliostoma canaliculatum containing a cationic neurotoxin (1, a disulfide-bonded dimer of 6-bromo-2-mercaptotryptamine) was studied. For comparison, hypobranchial gland homogenate was also examined by diffusion-NMR, an alternative approach for NMR mixture analysis. cITP/NMR concentrated the neurotoxin by almost 20-fold and isolated it from some of the other components present in the matrix. However, a minor component, likely a precursor or degradant, co-migrated with compound 1. Diffusion-NMR also did not resolve the two, indicating that the compounds possessed similar diffusion coefficients and electrophoretic mobilities. The strengths and limitations of the two approaches for NMR mixture analysis are discussed.