This study was conducted to prepare coaxial electrospun scaffolds of P3HB4HB/(gelatin + PVA) with various concentration ratios with P3HB4HB as the core solution and gelatin + PVA mixture as the shell solution; the mass ratios of gelatin and PVA in each 10 mL shell mixture were 0.6 g : 0.2 g (Group A), 0.4 g : 0.4 g (Group B), and 0.2 g : 0.6 g (Group C). The results showed that the pore size, porosity, and cell proliferation rate of Group C were better than those of Groups A and B. The ascending order of the tensile strength and modulus of elasticity was Group A < Group B < Group C. The surface roughness was Group C > Group B > Group A. The osteogenic and chondrogenic-specific staining showed that Group C was stronger than Groups A and B. This study demonstrates that when the mass ratio of gelatin : PVA was 0.2 g : 0.6 g, a P3HB4HB/(gelatin + PVA) composite scaffold with a core-shell structure can be prepared, and the scaffold has good biocompatibility that it may be an ideal scaffold for tissue engineering.