Chemically modified (K0.5Na0.5)NbO3 compositions with finely tuned polymorphic phase boundaries (PPBs) have shown excellent piezoelectric properties. The evolution of the domain morphology and crystal structure under applied electric fields of a model material, 0.948(K0.5Na0.5)NbO3-0.052LiSbO3, was directly visualized using in situ transmission electron microscopy. The in situ observations correlate extremely well with measurements of the electromechanical response on bulk samples. It is found that the origin of the excellent piezoelectric performance in this lead-free composition is due to a tilted monoclinic phase that emerges from the PPB when poling fields greater than 14 kV/cm are applied. 2013 AIP Publishing LLC.