The electric field response of the lead-free solid solution (1−x)Bi0.53Na0.47TiO3–xBaTiO3 (BNT–BT) in the higher BT composition range with x = 0.12 was investigated using in situ synchrotron X-ray powder diffraction. An introduced Bi-excess non-stoichiometry caused an extended morphotropic phase boundary, leading to an unexpected fully reversible relaxor to ferroelectric (R–FE) phase transformation behavior. By varying the field frequency in a broad range from 10−4 up to 102 Hz, BNT–12BT showed a frequency-dependent gradual suppression of the field induced ferroelectric phase transformation in favor of the relaxor state. A frequency triggered self-heating within the sample was found and the temperature increase exponentially correlated with the field frequency. The effects of a lowered phase transformation temperature TR–FE, caused by the non-stoichiometric composition, were observed in the experimental setup of the freestanding sample. This frequency-dependent investigation of an R–FE phase transformation is unlike previous macroscopic studies, in which heat dissipating metal contacts are used.