The rapid development of piezoelectric sensors has been studied extensively, owing to their good flexibility, wearability, high sensitivity and low cost. However, some inorganic materials with good piezoelectricity cannot make sensors flexible, and the organic materials with good flexibility have a weak output electrical signal and low strength. In order to explore and optimize the preparation technology of piezoelectric sensors, a BaTiO3@polyacrylonitrile (PAN)/poly(vinylidene fluoride) (PVDF) nanofibrous composite membrane (NCM) was prepared by cross-electrospinning technology and the central combination design (CCD) method. The morphology, structure, hydrophobicity, mechanical properties and piezoelectricity of the BaTiO3@PAN/PVDF NCMs were investigated. The BaTiO3@PAN/PVDF NCMs had the better hydrophobicity and mechanical properties compared with the pure PAN/PVDF NCM. The 5BaTiO3@PAN/PVDF NCM designed by CCD had a more uniform fiber diameter, and a more stable output voltage with a 46% improvement. With the help of cross-electrospinning technology and the CCD method, the NCM will be outstanding for the development of fabricating flexible wearable piezoelectric sensors.