The carbon film based ring-disk dual electrodes in the thin-layer radial flow cell are used as the dual electrochemical detector (DECD) for liquid chromatography (LC) to determine the monoamine neurotransmitters. Cyclic voltammetric experiments show there has great difference in the reversibility of the oxidative reactions of dopamine and ascorbate. Therefore the ring-disk dual electrode arrangement in the radial flow cell can effectively remove the interference of ascorbate and determine dopamine in the LC-DECD. In order to obtain the better collection efficiency (CE) and better peak current of analytes in the LC-DECD, several operational parameters have been investigated: flow rate, pH and the working potentials. Under the optimum conditions, the method shows a good stability and reproducibility to determine dopamine (DA), norepinephrine (NE), 5-hydroxytryptamine (5-HT), epinephrine (E) and 3,4-dihydroxyphenylacetic acid (DOPAC). The limits of detection are 0.1 pmol for DA, 0.1 pmol for NE, 0.1 pmol for 5-HT, 1.0 pmol for E and 0.1 pmol for DOPAC. The application of this method, coupled with microdialysis sampling, for the in vivo determination of the monoamine neurotransmitters in the striatum of the rat brain is satisfactory.