BiFeO₃ (BFO) microspheres were synthesized by a facile hydrothermal method. The optical absorption spectrum indicates that on site Fe³⁺ crystal-field transitions and the charge transfer excitations can be observed. Magnetic measurements show a spin-glass behavior and room temperature weak ferromagnetism. The surface photovoltage spectroscopy of the BFO shows two response peaks centered at about 370 and 400 nm, respectively. Under an ambient atmosphere, the maximum surface photovoltage of the BFO reaches 180 μV with the bias (+2 V) and is three times larger than that with zero bias. It is found that the surface photovoltage response intensity increases with an increase in applied bias, regardless of positive or negative bias. It is suggested that the surface photovoltaic properties are related to both the depolarization field owing to ferroelectric polarization and the build-in electric field due to the Schottky barrier. The micro-process and the physical mechanism of the separation of photogenerated charges for BFO are fully explained.