Blends of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) and poly(D,L-lactic acid) (PDLLA) with different ratios were fabricated into fibrous membranes by electrospinning processes. Suggested by DSC, WAXD, and SAXS results, the molecular chains of PHBHHx and PDLLA were partially mixed in the amorphous phase, PDLLA didn't affect the growth of PHBHHx crystalline phase, and PDLLA was excluded from PHBHHx lamella stacks, i.e. in form of interstack segregation, in the blend fibrous matrix. The mechanical properties of the electrospun fibrous membranes depended on the orientation of fibers in the membranes. The electrospun membranes had higher elongation; furthermore, the tensile strength and modulus of the fibers within the membranes were higher than the corresponding cast membranes. As the content of PDLLA increased, the electrospun fibrous membranes of the blends showed higher elongation and lower tensile modulus due to the decreased number of lamellae. According to the change of molecular weight distribution, both PHBHHx and PDLLA portions in the electrospun blend membranes followed bulk erosion and PDLLA degraded faster than PHBHHx during the degradation process. The morphology change of the electrospun fibrous blends during the hydrolytic degradation indicated that the degradation behaviors were strongly influenced by the miscibility and the structural phase segregation of PHBHHx/PDLLA blend in the electrospun fibers. (C) 2011 Elsevier Ltd. All rights reserved.