In this study, poly(vinyl alcohol) were cross-linked with boron in varying concentrations and blend fibers were obtained with diameters ranging from 0.3 mu to 4.0 mu m with the use of electrospinning process. The resulting product was characterized by SEM, DSC, and FT-IR techniques. There is no beading tendency in either boron doped or undoped fibers. When the amount of boric acid in PVA solutions was increased the conductivity of the polymer decreased. The data indicated the existence of boron oxide in the polymeric structure and the formation of B-O-C bond. SEM micrographs reveal that higher viscosity favors the formation of thicker fibers. Boron addition seems to disturb the easy detachment of the fibers from the tip of the Taylor Cone.