By the conventional solid state reaction method, a small amount of lithium fluoride (LiF) was used as the sintering promoter to improve the sintering and piezoelectric characteristics of (Ba0.95Ca0.05)(Ti0.93Sn0.07)O-3 (BCTS) lead-free piezoceramic sheets. Using X-ray diffraction (XRD) and a scanning electron microscope (SEM), the inferences of the crystalline and surface microstructures were obtained and analyzed. Then, the impedance analyzer and d(33)-meter were used to measure the dielectric and piezoelectric characteristics. In this study, the optimum sintering temperature of the BCTS sheets decreased from 1450 degrees C to 1390 degrees C due to LiF doping. For the 0.07 wt % LiF-doped BCTS sheets sintered at 1390 degrees C, the piezoelectric constant (d(33)) is 413 pC/N, the electric-mechanical coupling coefficient (k(p)) is 47.5%, the dielectric loss (tan ) is 3.9%, and the dielectric constant (epsilon(r)) is 8100, which are all close to or even better than that of the pure undoped BCTS ceramics. The Curie temperature also improved, from 85 degrees C for pure BCTS to 140 degrees C for BCTS-0.07 LiF sheets. Furthermore, by using the vibration system and fixing 1.5 g tip mass at the end of the sheets, as the vibration frequency is 20 Hz, the proposed piezoelectric ceramic sheets also reveal a good energy harvesting performance at the maximum output peak voltage of 4.6 V, which is large enough and can be applied in modern low-power electronic products.