Polystyrene nanofibres were electrospun with the inclusion of cationic surfactants, dodecyltrimethylammonium bromide (DTAB) or tetrabutylammonium chloride (TBAC), in the polymer solution. A small amount of cationic surfactant effectively stopped the formation of beaded fibres during the electrospinning. The cationic surfactants were also found to improve the solution conductivity, but had no effect on the viscosity. Only DTAB had an effect on the surface tension of the polymer solution, the surface tension decreasing slightly with an increase in the concentration of DTAB.