Bismuth sodium titanate (BNT)-derived materials have seen a flurry of research interest in recent years because of the existence of extended strain under applied electric fields, surpassing that of lead zirconate titanate (PZT), the most commonly used piezoelectric. The underlying physical and chemical mechanisms responsible for such extraordinary strain levels in BNT are still poorly understood, as is the nature of the successive phase transitions. A comprehensive explanation is proposed here, combining the short-range chemical and structural sensitivity of in situ Raman spectroscopy (under an applied electric field and temperature) with macroscopic electrical measurements. The results presented clarify the causes for the extended strain, as well as the peculiar temperature-dependent properties encountered in this system. The underlying cause is determined to be mediated by the complex-like bonding of the octahedra at the center of the perovskite: a loss of hybridization of the 6s2 bismuth lone pair interacting with the oxygen p-orbitals occurs, which triggers both the field-induced phase transition and the loss of macroscopic ferroelectric order at the depolarization temperature.