Abstract Bismuth ferrite thin films were prepared via sol–gel spin-coating method and the effects of annealing temperature on microstructure, optical, ferroelectric and photovoltaic properties have been investigated. The results show that the bismuth ferrite thin films annealed at 550 °C is single phase and the grain size increases with the rise of annealing temperature. The band gap of bismuth ferrite thin films annealed at 550–650 °C is between 2.306 eV and 2.453 eV. With the rise of the annealing temperature, the remnant polarization gradually decreases and the coercive electric field increases. The short circuit photocurrent density decreases with the rise of annealing temperature, and the open circuit photovoltage and the power conversion efficiency of bismuth ferrite thin films annealed at 550 °C are higher than the thin films annealed at higher temperature.