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Summary: In order to produce nanometer‐sized fibers at an industrial scale, not only the morphology but also the production rate of fibers is important. The effect of solvent properties and functionality on the production rate of electrospun PS nanofibers was investigated using eighteen different solvents. The solution concentration was varied between 10 and 30% w/v. Electrospinning of PS solutions was carried out at various applied voltages and tip‐to‐collector distances The production rate of the obtained PS nanofibers was quantified in terms of electrospinnability. We found that the chance for the resulting PS solution to be spinnable is greater for solvents with high dipole moment and low viscosity. The solvent that provided the highest electrospinnability for polystyrene was DMF and the functionalities that promoted high dipole moment and thus high spinnability were the carbonyl group and the nitrogen group with free electrons. General guidelines for choosing suitable solvents for successful production of electrospun nanofibers have also been proposed.