Electroactive biomaterials can influence the microenvironment between cells and a material’s surface by controlling surface electrical signals, thereby affecting cellular physiological activities. As the most commonly used ferroelectric polymer, Poly(vinylidene fluoride-trifluoroethylene) (PVTF) has attracted widespread attention due to its good stability, biocompatibility and mechanical properties. However, it has limitations such as non-degradability. In this study, PVTF nanoparticles (PVTF NPs), prepared using a phase separation method, were compounded with polylactide (PLA) to prepare PVTF NPs/PLA composite membrane (PN/PLA), which simultaneously achieved electroactivity and degradability. PVTF NPs containing ferroelectric β phase were evenly distributed on the PLA substrate, forming negative potential spots through corona polarization. The PLA substrate gradually degraded in a simulated body fluid environment. The negative surface potential provided by PVTF NPs in PN/PLA enhanced the adhesion, proliferation, and early-stage osteogenic differentiation of bone marrow mesenchymal stem cells (BMSCs). The electrical bioactivity and degradability could be joined together in this study, which is promising for tissue regeneration biomaterials, such as guided bone regeneration membrane.