In this study, electrospun nanofibers of polyurethane were prepared utilizing a new solvent system made of chloroform/methanol. Also, we planned to assess effects of four important parameters on diameter of electrospun polyurethane nanofibers using Artificial Neural Networks (ANNs). The parameters investigated included flow rate of syringe pump, distance of spinneret to collector, applied voltage and concentration of polymer solution. Diameter of obtained electrospun nanofibers was measured using scanning electron microscopy (SEM). Results showed that flow rate and distance had reverse relation with fiber diameter, while applied voltage and concentration of polymer solution directly affected the diameter. Also, polymer concentration was shown to be the dominant factor here.