Polymer-based lead-free piezoelectric composites provide environmentally friendly and scalable space for energy conversion and structural health monitoring. In this paper, multi-walled carbon nanotubes (MWCNT)-BaTiO3/polyvinylidene fluoride (PVDF) piezoelectric composite films for energy harvesting, sensing, and localization were prepared. The highest β-phase content of 90.21% in PVDF composite nanofibers was achieved owing to the synergistic effect of MWCNT and BaTiO3 nanoparticles. The open-circuit voltage of the flexible piezoelectric nanogenerator based on interdigital electrodes reached 11.4 V at 2 Hz and a bending strain of 4 mm with an optimal power and power density of 8.67 μW and 1.16 μW/cm2, respectively, and can light up to 8 LED lights simultaneously. The output voltage did not decay during 1800 cycles, which met the power and stability requirements of a commercial capacitor. In addition, the prepared piezoelectric sensors exhibited anisotropy and high sensitivity. They had a maximum amplitude sensitivity of 93 dB, which was superior to the reported PVDF-TrFE sensors and suitable for low-frequency signal monitoring in the range of 20–40 kHz. Localization accuracy was greater than 90% in linear and planar localization tests, demonstrating the potential of preparing acoustic emission sensors. These properties facilitate the reduction of the quantity of sensors required to identify the source of damage.