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The effects of rheological properties on the electrospun fiber structure of polyvinyl alcohol (PVA) with ultra high molecular weight (UHMW) and high hydrolysis degree have been studied in this article.Hydrazine salt was used to modify the rheological properties of PVA aqueous solution in order to facilitate electrospinning.Rheological properties of the solution and fiber morphology were investigated by a rheometer and a scanning electron microscope respectively.