A technique for synthesizing vanadium pentoxide microand nanofibers from vanadyl acetylacetonate by electrospinning is described, and the effect of the synthesis conditions on the fiber parameters is studied. The model of motion of a viscous dropping liquid with a finite electrical conductivity in a strong electrostatic field is shown to be applied to the formation of fibers from vanadyl acetylacetonate. A switching effect induced by a metal-insulator transition is revealed in the fibers.