The presence of a variety of structural variants in BiFeO3 thin films give rise to exotic electric-field-induced responses and resulting electromechanical responses as large as 5%. Using high-resolution X-ray diffraction and scanning-probe-microscopy-based studies the numerous phases present at the phase boundaries are identified and an intermediate monoclinic phase, in addition to the previously observed rhombohedral- and tetragonal-like phases, is discovered.