We investigated the new solid-phase microextraction method by high-performance liquid chromatography with electrochemical detection for the analysis of biogenic amines. The Carbowax-Templated Resin 50 mu m (purple) fibre coating offers good performances for dopamine and serotonin separation, i.e., good selectivity and high sensibility (0.1 mu g l(-1)). We also tested this fibre for biogenic amines quantification of rat striatum, The coating seems to be selective towards the amines and has low affinity for the metabolites, allowing a good separation and preventing drawbacks from the biological matrix. These first results obtained using this original separation method offer large perspectives of application to many biological samples.