The quality of electrospun poly(ethylene oxide) (PEO) nanofibrous mats are subject to a variety of input parameters. In this study, three parameters were chosen: molecular weight of PEO (100, 300, 600, and 1000 kg/mol), PEO concentration (in distilled water), and shear viscosity of PEO solution. Two relations free of any adjustable parameters were derived. The first, describing the initial stage of an electrospinning process expressing shear viscosity using PEO molecular weight and concentration. The second, expressing mean nanofiber diameter using concentration and PEO molecular weight. Based on these simple mathematical relations, it is possible to control the mean nanofiber diameter during an electrospinning process.