The method of preparation of polymer solutions significantly influences the quality of the corresponding electrospun nanofibrous webs. However, this factor is often ignored, and in a majority of presentations concerning the electrospinning process, the applied method is not mentioned. This paper compares the influence of magnetic stirring, vibrational shaking and ultrasonication on a solution of poly(ethylene oxide) in distilled water. Along with the methods of preparation, other parameters were altered such as concentration, intensity of mixing and molecular weight. The best results from the viewpoint of electrospinning were achieved with moderate magnetic stirring.