The structure, electrical properties, and depoling mechanism of the (0.95-x)BiScO3-xPbTiO3-0.05Pb(Zn1/3Nb2/3)O3 (BS-xPT-PZN, x=0.54–0.70) compositions close to the morphotropic phase boundary (MPB) have been systematically investigated as a function of PbTiO3 content (x). The phase approached from the rhombohedral toward the tetragonal phase when the PbTiO3 contents increased. The composition with high PT content exhibited normal ferroelectric behavior while it showed a diffused phase transition characteristic as PT decreased. In the vicinity of the MPB, the ceramics showed enhanced piezoelectric, electromechanical, and ferroelectric properties with piezoelectric constant d33=490 pC/N, planar electromechanical coupling factors kp=57.4%, remnant polarization Pr=40.1 μC/cm2, and coercive field Ec=28.5 kV/cm with a high transition temperature Tm∼417 °C, respectively. The thermal depoling experiments of the polarization for samples with different phase structures were investigated and the possible depoling mechanism was discussed.