This study reports the fabrication and characterization of poly(vinyl alcohol) (PVA) and gelatin (Gel)-based nanofiber membranes cross-linked with citric acid (CA) by a green electrospinning method in which nano 45S5 bioglass (BG) and urea were incorporated. Various combinations of PVA, gelatin, and BG were prepared, and nanofiber membranes with average fiber diameters between 238 and 595 nm were fabricated. Morphological, chemical, and mechanical properties, porosity, swelling, water retention, and water vapor transmission rate of the fabricated membranes were evaluated. PVA:Gel (90:10), 15% CA, and 3% BG were determined as the optimum blend for nanofiber membrane fabrication via electrospinning. The membrane obtained using this blend was further functionalized with 10% w/w polymer urea coating by the electrospray method following the cross-linking. In vitro biocompatibility tests revealed that the fabricated membranes were all biocompatible except for the one that functionalized with urea. In vivo macroscopic and histopathological analysis results of PVA/Gel/BG and PVA/Gel/BG/Urea treated wounds indicated increased collagenization and vascularization and had an anti-inflammatory effect. Furthermore, careful examination of the in vivo macroscopic results of the PVA/ Gel/BG/Urea membrane indicated its potential to decrease uneven scar formation. In conclusion, developed PVA/Gel/BG and PVA/Gel/BG/Urea electrospun membranes with multifunctional and biomimetic features may have the potential to be used as beneficial wound dressings.