Fibrous membranes of aligned poly (hydroxybutyrate-co-hydroxyvalerate) (PHBV) fibers have been made through electrospinning. A high-speed rotating drum was used as the fiber collector while the electric field was manipulated by using five knife-edged auxiliary electrodes. It was found that a high drum rotating speed of 3000 rpm could lead to a nearly perfect alignment of PHBV fibers during electrospinning. Multilayered fibrous structures with each layer having a different direction of fiber alignment could also be constructed through electrospinning. The electrospun PHBV fibers were further modified by incorporating carbonated hydroxyapatite (HA) nanospheres (up to 20% of HA) in the fibers. The fibrous membranes made of aligned PHBV fibers and made of HA/PHBV composite fibers should be very useful for the tissue engineering of different human body tissues.