In this study PVDF-BaTiO3 and PVDF-BaTiO3-Ag composite fibers were prepared by the electrospinning technique. X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, and Raman spectroscopy results showed that an increase in the amount of BaTiO3 up to 0.8 wt% increases the amount of the β phase ~90%. BaTiO3 particles prepared by sol-gel method were irradiated by ultraviolet light in silver nitrate solution for 2, 6, and 10 min to precipitate silver on BaTiO3 particles. Electrospun PVDF-BaTiO3-Ag fibers showed an increase in the output voltage (1.78(12) mV) compared to pristine PVDF and PVDF-BaTiO3 composite fibers (1.48(26) mV) upon applying 1.2 N force at 5 Hz frequency. According to XRD and FTIR spectroscopy, the amount of the β phase in each sample increased by increasing the silver content. Such enhancement in the piezoelectric output voltage of PVDF-BaTiO3-Ag fibers is attributed to the increase in the amount of β phase as well as the existence of silver as a conductive phase.