Nanofibres were electrospun from bicomponent poly(vinyl alcohol) (PVA) and modified cationic starch (CS) mixed solutions PVA/CS with different mass ratio (75/25, 50/50, 35/65) at total concentration 12 wt% for all polymer compositions. Electrospinning technique using rotating electrode with tines was used in this paper due to obtain better results in previously described work. In this work the effect of prepared polymer solution compositions on the structure and morphology of nanofibers was investigated. Moreover, pure PVA was used with the condition that the results can be compared with bicomponent PVA/CS solutions. Analyzing the structure and morphology of formed nanofibers webs it was noticed that lower diameter was formed from the PVA/CS with mass ratio 50/50 and 35/65. Also, it is possible to see that lower density of nanofibers web was formed compared with results of the pure PVA solution.