Poly 3-hydroxybutyrate (PHB) as a kind of polysaccharides has been proved promising for tissue engineering because of its biocompatibility and biodegradability. But its poor mechanical properties and hydrophilicity limit its application. In order to explore a new useful porch to improve the performance of PHB-based GTR membrane, membrane composed of nano-HA / PHB composite was manufactured through the air/jet electrospinning process which can potentially generate nanometer scale diameter fibers and enlarge surface area of materials while maintaining high porosity. Successively, the biomineralization behavior of the membrane in supersaturated calcification solution (SCS) was studied. The Results of this investigation show that the successfully manufactured porous nano-HA/PHB membrane has high activity in SCS and its ability of inducing the formation of mineral crystal in vitro than that of the unfilled PHB membrane. It can be concluded that the addition of nano-HA and the novel technology could improve the performance of the PHB-based GTR membrane.