Electrospinning of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) in chloroform was investigated to develop non-woven biodegradable nanofibrous structures for tissue engineering. Ultrafine PHBV fibers were obtained by electrospinning of 20 wt.% PHBV solution in chloroform and the resulting fiber diameters were in the range of 1.0-4.0 microm. When small amounts of benzyl trialkylammonium chlorides were added to the PHBV solution, the average diameter was decreased to 1.0 microm and the fibers were amounted in a straight shape. Conductivity of the PHBV solution was a major parameter affecting the morphology and diameter of the electrospun PHBV fibers. PHBV non-woven structures electrospun with salt exhibited a higher degradation rate than those prepared without salt probably due to the increase of surface area of PHBV fibers.