We proposed an approach using a multi-walled carbon nanotubes (MWCNTs)/Nafion composite coating as a working electrode for the electrochemically enhanced solid phase microextraction (EE-SPME) of charged compounds.Suitable negative and positive potentials were applied to enhance the extraction of cationic (protonated amines) and anionic compounds (deprotonated carboxylic acids) in aqueous solutions, respectively.Compared to the direct SPME mode (DI-SPME) (without applying potential), the EE-SPME presented more effective and selective extraction of charged analytes primarily via electrophoresis and complementary charge interaction.The experimental parameters relating to extraction efficiency of the EE-SPME such as applied potentials, extraction time, ionic strength, sample pH were studied and optimized.The LDRs of developed EE-SPME-GC for selected amines spanned three orders of magnitude (0.005-1 μg mL-1) with R2 larger than 0.9933, and the limits of detection were in the range of 0.048~0.070 ng mL-1.All of these characteristics demonstrate that the proposed MWCNTs/Nafion EE-SPME is an efficient, flexible and versatile sampling and extraction tool which is ideally suited for use with chromatographic methods.