Ultra-thin fibers, consisting of blends of a PPE derivative and polystyrene, with average diameters ranging from 430 to 1 200 nm, were produced by electrospinning. . The electro-spinnability was significantly improved by adding pyridinium formate to the spinning solution. FT-IR spectroscopy was used to confirm the composition of the electrospun fibers and their morphology was probed by SEM. The optical properties of the as-prepared solutions, pristine and annealed fibers, and corresponding spin-coated and solution-cast films were investigated by UV-vis spectroscopy. A comparison of the PL emission spectra revealed aggregation of PPE molecules in the electrospun materials but the extent of aggregation can be reduced if the materials are annealed above the glass transition temperature.