Structurally coherent and chemically abrupt interfaces formed between polar and nonpolar perovskite oxides provide an ideal platform for examining the purely electronic reconstruction known as the polar catastrophe and the emergence of mobile or bound charges at the interface. The appearance of mobile charges induced by the polar catastrophe is already established in the LaAlO_{3}/SrTiO_{3} heterojunctions. Although not experimentally verified, the polar catastrophe can also lead to the emergence of spontaneous polarization. We report that thin films of originally nonpolar LaFeO_{3} grown on SrTiO_{3} are converted to polar as a consequence of the polar catastrophe. The induced spontaneous polarization evokes photovoltaic properties distinct from conventional p-n junctions, such as a switching of the photocurrent direction by changing the interfacial atomic sequence. The control of the bulk polarization by engineering the interface demonstrated here will expand the possibilities for designing and realizing new polar materials with photovoltaic functions.