The use of cylindrical carbon ®ber microelectrodes (CFMEs) of various mm in length modi®ed with poly(3-methylthiophene) (P3MT) ®lms as amperometric microsensors for the LC-EC detection of catecholamines is reported. Cyclic voltammetry at the modi®ed microelectrodes of dopamine, epinephrine, catechol, serotonin and ascorbic acid showed electrocatalytic ability of the modi®ed surface. This allowed the application of low potentials (0.35 V) for the amperometric detection of the above-mentioned compounds. Flow injection measurements carried out using a 2:98 vav methanol:0.025 mol L À1 H 2 PO 4 À aHPO 4 2À solution of pH 7.0, showed no evidence of fouling of the modi®ed microelectrode surface. No cleaning or regeneration treatment was needed when working with the same polymer modi®ed microelectrode during the whole working day. Moreover, RSD values for i p lower than 5 % were obtained when amperometric measurements were carried out with three different P3MT-coated CFMEs. These modi®ed microelectrodes have also shown to be suitable for amperometric detection in HPLC. A mobile phase composed of 2:98 % methanol:phosphate buffer solution of pH 7.0 allowed a good separation of mixtures of ascorbic acid, epinephrine, dopamine, serotonin and catechol with detection limits ranging between 14 and 48 pmol. Furthermore, as an application, the determination of those compounds in spiked serum samples, was accomplished with good results.