Mixed phases with stripe patterns are considered as a prerequisite for remarkable piezoelectric properties in epitaxial BiFeO3 (BFO) thin films. Among the mixed phases in BFO epitaxial thin films, the vital role in achieving high piezoelectric response is attributed to the intermediate S-polymorph that bridges the transition between rhombohedral and tetragonal phases. However, the correlation between the S-phase and the piezoelectric strain in mixed-phase BFO has not been understood well due to the lack of a probe technique that can investigate the structural and electromechanical variations simultaneously. Here, using the time-resolved X-ray microdiffraction technique, we investigate the electric field induced phase transformation dynamics of a mixed-phase epitaxial La-doped BFO (BLFO) thin film. The BLFO thin film exhibits phase transformations between monoclinic M-C and tilted M-C, S/tilted S (S-tilt) phases under an applied electric field. Among the competing phases, we found that the S- or tilted S-phases exhibit the highest piezoelectric strain variation up to 0.7% at an electric field pulse of strength 1.3 MV/cm and width 5 mu s. The present study correlates the high piezoelectric response in mixed-phase BLFO thin films with the presence of S/S-tilt -phases, which offers a useful pathway into designing strain-engineered ultra-high piezoelectric BFO thin films. (C) 2021 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.