The cross-linked poly-2-isopropyl-2-oxazolines (PiPrOx) differing in cross-linker content have been synthesized and characterized by light scattering, chromatography, and rheometry. The dramatic influence of the cross-linker content on solubility and uni- or bimodality was observed. For the first time, the interpolymer complex of cross-linked PiPrOx with polyethylene oxide is manufactured in fibrous form by the electrospinning method. The role of intermolecular hydrogen bonds in the structure and properties of electrospun fibers (EF) was studied by infrared spectroscopy, differential scanning calorimetry, and scanning electron microscopy. It was established that these interactions allow to obtain a uniform fibrous membrane. At the same time, hydrogen bonding is responsible for the self-organization of PiPrOx in water.