Biocompatible polyvinyl alcohol/polyethylene glycol and polyvinyl alcohol/polypropylene glycol copolymer mats were prepared by electrospinning. The composite fiber mats were subjected to detailed physical analysis complemented by scanning electron microscopy and Fourier transformations infrared spectroscopy. Scanning electron microscopy images showed that the morphology and diameters of the fibers were mainly affected by the types of polymers and their copolymer compositions. Microbial culture results showed that among the tested fibrous mats polyvinyl alcohol/50% polyethylene glycol gave the best results in preventing the cell attachment and proliferation. This novel electrospun matrix would be used as potential wound dressing material for skin regeneration.