Nanofibers were electrospun from bicomponent poly(vinyl alcohol) (PVA) and modified cationic starch (CS) mixed solution PVA/CS with different mass ratios (75/25, 50/50 and 35/65) at a total concentration of 12 wt% for all polymer compositions. For comparison, pure PVA solution was used. Electrospinning technique Nanospider (Elmarco, Czech Republic) with a rotating electrode with tines was used to obtain nanofibrous web. The influence of prepared polymer solution compositions on the structure and morphology of nanofibers and webs were investigated. Analyzing the structure and morphology of the formed nanofiber webs, it was noticed that the fineness nanofibers were formed from the PVA/CS solution with a mass ratio of 50/50. This ratio of solution also lets us to obtain the nanofibrous web with less sticked nanofibers on spunbond. The increase in the CS ratio by more than 50/50 had a negative influence on the diameter of nanofibers and the structure of nanofibrous web.