For the first time, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) nanofibrous membrane has been fabricated via electrospinning method. To improve the electrospinnability and reduce the diameter of fibers, the solvent and salt additives were used that affected on the parameters including such as the viscosity and the conductivity of the electrospinning solution for poly(3-hydroxybutyrate-co-3-hydroxyhexanoate). Since the additional salts should be removed, it could be inferred that the co-solvent system was predominant to prepare the nanofibrous poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) membrane. This biodegradable nanofibrous poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) membrane has a great potential to be used in the various application fields such as tissue engineering, implants, packaging materials, agriculture, and so on.