Titanium (Ti)-based implants are among the most advantageous biomaterials in both orthopedic and dental applications, owing to their excellent properties and biocompatibility. However, their bioinert surface poses challenges to osteointegrity, raising concerns about implant loosening. The present study examines the effect of surface modification of Ti by applying a bioactive piezoelectric fibrous coating comprised of electrospun poly(L-lactide) (PLLA) as a biodegradable piezopolymer and varying amounts of hydroxyapatite (HA) filler (5−20 wt%) as an osteoconductive piezoceramic. According to SEM micrographs, adding HA increased the fiber diameter, porosity, and pore size of the fibrous structure. Furthermore, peeling test of the fibrous coating demonstrated that applying a polydopamine (PDA) coating before electrospinning onto the Ti substrate effectively enhanced the adhesion strength of the coating. Additionally, the PLLA/HA composite coating exhibited increased piezoelectric properties, with piezoresponse rising from 2.41 ± 0.192 mV/N (5 wt% HA) to 5.42 ± 0.192 mV/N (20 wt% HA). Similarly, PLLA/HA coatings showed superior apatite-forming ability in simulated body fluid (SBF) at 7 and 28 days, with significantly higher calcium-phosphate deposition and a Ca/P ratio close to natural bone, surpassing the neat PLLA coating and bare Ti substrate. Finally, testing with MG-63 cell lines indicated that fibrous composite coatings enhance cell support, demonstrating optimal alkaline phosphatase (ALP) secretion levels and positive cell attachment. Consequently, the surface-modified Ti with fibrous PLLA/HA coating emerges as a promising strategy for the clinical treatment of bone defects.