We report on the visualization of n-p junctions formed by oxygen vacancy movement under the application of an electric field in a Ca-doped BiFeO3 thin film through spatially resolved scanning photocurrent mapping. The photocurrent mapping, in conjunction with the spectroscopic approach, provides clues to local electronic structures and defect levels associated with oxygen vacancies. These observations provide insights into the spatial redistribution of oxygen vacancies in an electric field. (C) 2013 American Institute of Physics. [http://dx.doi.org/10.1063/1.4774381]