Bismuth ferrite (BFO) nanofibers were synthesized via a solgel-based electrospinning process followed by thermal treatment. The influences of processing conditions on the final structure of the samples were investigated. Nanofibers prepared under optimized conditions were found to have a perovskite structure with good quality of crystallization and free of impurity phase. Ferroelectric and piezoelectric responses were obtained from individual nanofiber measured on a piezoelectric force microscope. A prototype photovoltaic device using laterally aligned BFO nanofibers and interdigital electrodes was developed and its performance was examined on a standard photovoltaic system. The BFO nanofibers were found to exhibit an excellent ferroelectric photovoltaic property with the photocurrent several times larger than the literature data obtained on BFO thin films.