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This paper focuses on the mechanism of electrochromatography (EC), i.e. the electrotransport of analytes driven by the applied electric field, and proposes that two distinct mechanisms are involved in EC. The first involves the migration of analytes as large molecules in the driven solvent, and the second involves the emission of electrochromatogram (ECG) from a template-molecule-coated, charged surface (and reverse) to the analytes. To investigate these mechanisms, EC behavior was analyzed in solution and on model-channels via capillary electrophoresis. In the latter, it was observed that the electrodes may induce electric double layer (EDL) formation at the tip of the capillary channel. The space charge behavior of the ECG was influenced by the surfaces of the electrodes. The presence of background electric field affects the migration of the template-molecule-coated, charged surface during EC. These surface effects on the ECG could be predicted by using theoretical calculations. ECG generation was observed for a wide range of conditions, including 0b46394aab