Three-dimensional random calcium ferrite, CaFe2O4, nanofibers (NFs) were successfully prepared via the electrospinning method. The effect of calcination temperature on the characteristics of the as-spun NFs was investigated. X-ray diffraction analysis showed that CaFe2O4 phase crystallized as a main phase at 700 degrees C and as a sole phase at 1000 degrees C. Field emission scanning electron microscopy emphasized that CaFe2O4 NFs were fabricated with diameters in the range of 50-150 nm and each fiber was composed of 20-50 nm grains. Magnetic hysteresis loops revealed superparamagnetic behavior for the prepared NFs. These NFs produced active hydroxyl radicals under simulated solar light irradiation making them recommendable for photocatalysis applications in water purification. In the meantime, these NFs can be easily separated from the treated water by applying an external magnetic field.