The aim of this tutorial review is to introduce to a broader readership the emerging technique of electrophoretic NMR (eNMR). The "electrophoretic" element of the technique refers to the fact that charged particles are induced to flow by the application of an electric field. This flow is measured using pulsed-gradient spin-echo NMR (PGSE-NMR). The great potential of this experimental approach is the fact that NMR is chemically selective and non-invasive. eNMR, especially when combined with the more established PGSE-NMR experiment, may therefore be used to quantify the structure of multi-component systems via the dynamics and charge of each species within a complex mixture. Accordingly, eNMR is likely to be of great significance for colloid scientists, biologists, technologists and formulation scientists.