We report the first direct evidence that the morphotropic phase boundary in ferroelectric materials, along with the associated strong piezoelectricity, can be created, destroyed, or even replaced by another morphotropic phase boundary through phase transitions during electrical poling. The real-time evolution of crystal structure and domain morphology during the poling-induced phase transitions in (Bi(1/2)Na(1/2))TiO3}BaTiO3 is observed with in situ transmission electron microscopy. These observations elucidate the microstructural origin of the macroscopic piezoelectricity's dependence on the poling field and previously unexplained strain behaviors. This study demonstrates that the ferroelectric-to-ferroelectric transitions during the poling process can completely alter the morphotropic phase boundaries and, hence, must be comprehensively investigated when interpreting the microscopic mechanism of macroscopic piezoelectric behaviors.