The use of nanomaterials as an electroactive medium has improved the performance of bio/chemical sensors, particularly when synergy is reached upon combining distinct materials. In this paper, we report on a novel architecture comprising electrospun polyamide 6/poly(allylamine hydrochloride) (PA6/PAH) nanofibers functionalized with multiwalled carbon nanotubes, used to detect the neurotransmitter dopamine (DA). Miscibility of PA6 and PAH was sufficient to form a single phase material, as indicated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), leading to nanofibers with no beads onto which the nanotubes could adsorb strongly. Differential pulse voltammetry was employed with indium tin oxide (ITO) electrodes coated with the functionalized nanofibers for the selective electrochemical detection of dopamine (DA), with no interference from uric acid (UA) and ascorbic acid (AA) that are normally present in biological fluids. The response was linear for a DA concentration range from 1 to 70 mu mol L-1, with detection limit of 0.15 mu mol L-1 (S/N = 3). The concepts behind the novel architecture to modify electrodes can be potentially harnessed in other electrochemical sensors and biosensors.