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The application of chitosan (Ch) as a promising biopolymer with hemostatic properties and high biocompatibility is limited due to its prolonged degradation time, which, in turn, slows the repair process. In the present research, we aimed to develop new technologies to reduce the biodegradation time of Ch-based materials for hemostatic application. This study was undertaken to assess the biocompatibility and hemostatic and tissue-regeneration performance of Ch-PEO-copolymer prepared by electrospinning technique. Chitosan electrospinning membranes (ChEsM) were made from Ch and polyethylene oxide (PEO) powders for rich high-porous material with sufficient hemostatic parameters. The structure, porosity, density, antibacterial properties, in vitro degradation and biocompatibility of ChEsM were evaluated and compared to the conventional Ch sponge (ChSp). In addition, the hemostatic and bioactive performance of both materials were examined in vivo, using the liver-bleeding model in rats. A penetrating punch biopsy of the left liver lobe was performed to simulate bleeding from a non-compressible irregular wound. Appropriately shaped ChSp or ChEsM were applied to tissue lesions. Electrospinning allows us to produce high-porous membranes with relevant ChSp degradation and swelling properties. Both materials demonstrated high biocompatibility and hemostatic effectiveness in vitro. However, the antibacterial properties of ChEsM were not as good when compared to the ChSp. In vivo studies confirmed superior ChEsM biocompatibility and sufficient hemostatic performance, with tight interplay with host cells and tissues. The in vivo model showed a higher biodegradation rate of ChEsM and advanced liver repair.