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Electrospinning has emerged as one of the major technologies for designing and fabricating tissue engineering membranes. The resemblance of the electrospun fiber structure to blood capillaries endowed them with unique capabilities to mimic the native tissue biological characteristics, while the high surface‐to‐volume ratio enables them to exert a controlled release of drug directly to the exposed interstitial tissue. This research attempts to compare the characteristics of different electrospun polyvinyl alcohol/hyaluronic acid (PVA/HA) composite material nanofibrous membranes in order to identify the optimal material‐fabrication combination for wound dressing and skin tissue engineering applications. Far‐field electrospinning equipped with both rotatory and wire collectors is considered for membrane fabrication. PVA with different concentrations and molecular weights of HA are electrospun as nanofibrous membranes considering a voltage of 30 kV on both types of collectors. Comprehensive characterization is conducted including morphological, chemical, thermal, mechanical, and in vitro mucoadhesion analysis. In vitro cell viability/proliferation studies are also carried out and pointed out that the designed membranes are cytocompatible, and able to support keratinocytes proliferation. All these results proved that the fabricated PVA/HA nanofibrous membranes are suitable for wound dressing and skin tissue engineering applications, the optimal material‐fabrication combination is also determined. [ABSTRACT FROM AUTHOR]