Poly(vinyl alcohol) (PVA) is a biomaterial that has interesting features for applications in soft tissue replacement due to its similarities in the mechanical properties of such tissues. This paper describes the preparation and characterization of PVA fibers obtained by electrospinning and crosslinked with potassium persulfate as thermoinitiator. These PVA fibers were characterized by Scanning Electron Microscopy (SEM) and Optical Microscopy (OM) to analyze the morphology of the spun samples. Finally, Fourier Transform Infrared Spectroscopy (FTIR) and differential scanning calorimetry (DSC) were performed and the results showed that the biomaterial was partially cross-linked, which indicates a potential use for dermal regeneration applications. The morphology of the fibers indicated that structural changes occurred in the biomaterial after thermal crosslinking.