In the present study, the influence of electrical parameters of the pulsed electrospinning process, such as electrical voltage, frequency of the pulses and pulse duration on the structure of the nonwovens obtained was determined for the first time. It was found that all the parameters studied strongly influence the average diameter of the fibres obtained, and that the pulsed electrospinning process carried out under specific conditions makes it possible to obtain, among other things, bimodal nonwovens. In addition, a 23 factorial design was used to determine how the selected electrical parameters of the pulsed electrospinning process affect the structure of the resulting electrospun mats. It was shown, among other things, that by appropriately selecting the parameters of the electrospinning process, the thickness of the fibres can be controlled, resulting in nonwovens with the desired morphology.