The environmental regulations for lead-based materials have resulted in the piezoelectric energy harvester based on lead-free piezoelectric ceramics attracting increased attention. In this work, two different types of piezoelectric materials, Ba(Zr0.04Ti0.96)O3 and CuO-Ba(Zr0.04Ti0.96)O3 ceramics, have been employed for energy harvesters applications to replace lead-based energy harvesters. The BZT and CuO-BZT ceramics were prepared by the conventional solid solution method. The piezoelectric properties of CuO-BZT ceramics showed higher piezoelectric values (d33 = 302pC/N and g33 = 20.64mVm/N) than those of BZT ceramics: (d33 = 268pC/N and g33 = 19.11mVm/N). The BZT and CuO-BZT ceramics were stacked in a multilayered structure to form triple layers. The stored energy in the capacitors (3μF) for multilayered BZT and CuO-BZT were 1.72 and 2.67mJ/cm3, respectively. The energy harvesters based on the lead-free ceramics BZT and CuO-BZT were analyzed and compared.