This study aimed to develop Janus-, cross-network-, and coaxial-structured piezoelectric-conductive polymer nanofibers through electrospinning to mimic the piezoelectricity of bone and facilitate the conduction of electrical signals in bone tissue repair. These nanofibers were constructed using the piezoelectric polymer polyvinylidene fluoride, and the conductive fillers reduced graphene oxide and polypyrrole. The influence of structural features on the electroactivity of the fibers was also explored. The morphology and components of the various structural samples were characterized using SEM, TEM, and FTIR. The electroactivity of the materials was assessed with a quasi-static d33 meter and the four-probe method. The results revealed that the piezoelectric-conductive phases were successfully integrated. The Janus-structured nanofibers demonstrated the best electroactivity, with a piezoelectric constant d33 of 24.5 pC/N and conductivity of 6.78 × 10-2 S/m. The tensile tests and MIP measurements showed that all samples had porosity levels exceeding 70%. The tensile strength of the Janus and cross-network structures exceeded that of the periosteum (3-4 MPa), with average pore sizes of 1194.36 and 2264.46 nm, respectively. These properties indicated good mechanical performance, allowing material support while preventing fibroblast invasion. The CCK-8 and ALP tests indicated that the Janus-structured samples were biocompatible and significantly promoted the proliferation of MC3T3-E1 cells.