The phase separation of multiple competing structural/ferroelectric phases has attracted particular attention owing to its excellent electromechanical properties. Little is known, however, about the strain-gradient-induced electronic phenomena at the interface of competing structural phases. Here, we investigate the polymorphic phase interface of bismuth ferrites using spatially resolved photocurrent measurements, present the observation of a large enhancement of the anisotropic interfacial photocurrent by two orders of magnitude, and discuss the possible mechanism on the basis of the flexoelectric effect. Nanoscale characterizations of the photosensitive area through position-sensitive angle-resolved piezoresponse force microscopy and electron holography techniques, in conjunction with phase field simulation, reveal that regularly ordered dipole-charged domain walls emerge. These findings offer practical implications for complex oxide optoelectronics.