The correlation between structure and electrical properties of lead-free (1−x)(Bi1/2Na1/2)TiO3–xBaTiO3 (BNT-100xBT) polycrystalline piezoceramics was investigated systematically by in situ synchrotron diffraction technique, combined with electrical property characterization. It was found that the morphotropic phase boundary (MPB) between a rhombohedral and a tetragonal phase evolved into a morphotropic phase region with electric field. In the unpoled material, the MPB was positioned at the transition from space group R3m to P4mm (BNT-11BT) with optimized permittivity throughout a broad single-phase R3m composition regime. Upon poling, a range of compositions from BNT-6BT to BNT-11BT became two-phase mixture, and maximum piezoelectric coefficient was observed in BNT-7BT. It was shown that optimized electrical properties are related primarily to the capacity for domain texturing and not to phase coexistence.