Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) was used to fabricate micro- and nano-fibrous, non-woven mats by electrospinning for potential tissue engineering applications. The morphology and size of electrospun fibers were assessed systematically by varying the processing parameters. It was found that the diameter of the fibers produced generally increased with electrospinning voltage, needle diameter for the polymer jet and polymer solution concentration. Beaded fibers were readily produced at low PHBV concentrations, whereas the needle was blocked within a very short time during electrospinning when the PHBV concentration was too high. At the polymer concentration of 7.5 % w/v, it was shown that beadless PHBV fibers could be generated continuously by adjusting the electrospinning parameters to appropriate values. This study has clearly demonstrated that electrospinning can be an effective technique to produce PHBV micro- and nano-fibers. It has also been shown that composite fibers containing hydroxyapatite (HA) can be produced using the electrospinning technique.