Perovskite LaFeO₃ hollow fibers with porous walls have been synthesized using cotton as biotemplates and lanthanum nitrate and ferric nitrate solution as precursors and then sintered in air at different temperatures. Effect of calcination temperature on the catalytic and photocatalytic activity of LaFeO₃ hollow fibers towards the degradation of methylene blue dye was studied. Samples were characterized by X-ray powder diffraction (XRD), Transmission electron microscope (TEM), Scanning electron microscope (SEM) Brunauer–Emmett–Teller (BET), photoluminescence spectrum (PL), Zeta potential, and UV-Visible spectroscopy analysis. XRD, SEM, and TEM proved the successful synthesis of perovskite LaFeO₃ hollow fibers with crystalline size from 19.9 nm to 41nm. It is found that by increasing calcinations temperature, the catalytic and photocatalytic activity of LaFeO₃ hollow fibers increased.