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Background electrolyte solutions (BGEs) containing organic solvents are common alternatives to aqueous BGEs in capillary electrophoresis.Several general advantages of organic solvent over water have been asserted in the literature, such as the lower conductivity and consequent possibility of applying higher voltage, with the beneficial effects of increasing the efficiency and reducing the analysis time.This communication discusses the influence of two structurally similar organic solvents on both the electroosmotic flow in bare fused-silica capillary and the electrophoretic behaviour of model analytes.The two investigated solvents are 2,2,2-trifluoroethanol and ethanol which were independently employed as components of the hydro-organic background electrolyte solution.