The majority of piezoelectric ceramics based on Pb(Zr, Ti)O₃ (PZT) exhibit hysteretic behavior, which varies depending on various factors, including composition, microstructure and processing conditions. The ternary system 0.05Pb(Mn_1/3Sb_2/3)O₃–0.95Pb(Zr_0.52Ti_0.48)O₃ (5PMS-PZT) has shown attractive piezoelectric properties with superior thermal stability compared to pure Pb(Zr_0.52Ti_0.48)O₃, but the underlying mechanisms of its complex hysteretic behavior have not been fully clarified yet. This work further delves into the hysteretic aspects of 5PMS-PZT ceramics and describes hysteresis features that have not been yet reported for any known piezoelectric system. Four current peaks in I-E loops and S-E loops with unconventional shapes, which have a significant dependence on applied field amplitude, frequency and electrical history have been observed here. This peculiar hysteretic behavior is influenced by convoluted effects of domain switching, electric field-induced structural transitions, point defects and aging/de-aging processes, whose combinations lead to unique hysteresis features.