Piezoelectric materials, due to their ability to generate an electric charge in response to mechanical deformation, are becoming increasingly attractive in the engineering of bone and neural tissues. This manuscript reports the effects of the addition of nanohydroxyapatite (nHA), introduction of gold nanoparticles (AuNPs) via sonochemical coating, and collector rotation speed on the formation of electroactive phases and biological properties in electrospun nanofiber scaffolds consisting of poly(vinylidene fluoride) (PVDF). FTIR, WAXS, DSC, and SEM results indicate that introduction of nHA increases the content of electroactive phases and fiber alignment. The collector rotational speed increases not only the fiber alignment but also the content of electroactive phases in PVDF and PVDF/nHA fibers. Increased fiber orientation and introduction of each of additives resulted in increased SFE and water uptake. In vitro tests conducted on MG-63 and hiPSC-NSC cells showed increased adhesion and cell proliferation. The results indicate that PVDF-based composites with nHA and AuNPs are promising candidates for the development of advanced scaffolds for bone and neural tissue engineering applications, combining electrical functionality and biological activity to support tissue regeneration.