A neat electroactive freestanding non-woven mat was first prepared from poly(o-methoxyaniline) (POMA) using an electrospinning technique without blending or grafting. Results showed that a continuous fibre structure was obtained for high weight-average molecular weight (M) over bar (w) of POMA, i.e. POMA forced to become more soluble when synthesized in the presence of CaCl(2) and an alkoxyl-ring-substituted structure. By performing gel permeation chromatography and viscosity tests, we found that (M)double over bar(w) approximate to 69 000 g mol(-1) and concentrations were critical to the formation of beads or fibres. The electrospinning parameters that cause morphological changes were found by scanning electron microscopy. By comparing these with governing parameters such as viscosity, feeding rate, collector distance and applied voltage, uniform POMA fibres were produced from 5 wt% POMA solution at 20 kV with a feeding rate of 0.02 mL min(-1) and nozzle-to-collector distance of 12 cm. In addition, the electroactivity and mechanical strength of the neat electrospun non-woven mats were studied by electrochemical cyclic voltammogram and dynamic mechanical analysis, respectively. (C) 2011 Society of Chemical Industry