The piezoelectric properties of 0.65Pb(Zr_1-xTi_x)O₃-0.35Pb(Zn_1/6Ni_1/6Nb_2/3)O₃ (PZT_x-PZNN) ceramics with 0.530≤ x≤0.555 were investigated for application to piezoelectric energy harvesters. Although a morphotropic phase boundary (MPB) was found at approximately x＝0.545, the ceramic with the highest figure of merit (FOM) (d₃₃×g₃₃) was observed at a composition of x＝0.540. Values of this figure of merit, d₃₃×g₃₃, of 19.6 pm²/N and 20.2 pm²/N were obtained from PZT_0.540-PZNN ceramics sintered at 920℃ and 950℃, respectively. A high output power of 937 μW and a high power density of 3.3 mW/cm³ were obtained from unimorph-type piezoelectric energy harvesters fabricated using PZT_0.540-PZNN ceramic sintered at 920℃ for 4h.