Ferroelectric thin films of BaTiO3 have been successfully deposited on n‐type silicon substrates at temperatures above 500 °C by rf sputtering in an O2/Ar atmosphere. Analysis by x‐ray diffraction patterns show that films deposited at room temperature are amorphous. At temperatures above 500 °C, crystalline BaTiO3 films with a tetragonal structure are obtained. The polarization‐electric field (P‐E) hysteresis loops and a broad peak in the dielectric constant versus temperature curve at Curie point indicate that the rf sputtered BaTiO3 films are ferroelectric. An anomalous photovoltaic effect is observed in these thin films which is related to the remanent polarization of the material. The results on open‐circuit and short‐circuit measurements provide an important basis for a better understanding of the role of photovoltaic field, photovoltaic current, and the pyroelectric properties in photoferroelectric domain switching.