Nano-crystalline, CeCr1−xFexO3 (x = 0 and 0.05) compounds synthesized by a facile nitrate-solution combustion method are crystallized in orthorhombic, Pnma structure. Reitveld refinement of diffraction patterns reveal an expansion of lattice parameter and lattice volume after the substitution of Fe. Structural analysis evidences an increase in distortion in orthorhombic structure due to bending of Cr-O6 octahedra which is a sheer consequence of the lattice expansion. The optical band gap decreases from 2.9 to 2.6 eV due to the increase in particle size and decrease in strain after Fe substitution estimated from Williamson-Hall analysis. Besides the decrease in Neel temperature from 260 to 253 K after Fe incorporation, temperature-dependent magnetization exhibits some peculiar features such as compensation temperature, Tcomp, and spin reorientation temperature, TSR. While TSR enhances from 15 to 30 K, we observe two Tcomp at 13 and 110 K for x = 0.05 in contrast to only one Tcomp at 61 K for the pristine phase. Moreover, we for the first time demonstrate a stable switching behavior of magnetization by varying the external field in the same direction. The increase in Tcomp and TSR along with a decrease in band gap from 2.9 eV to 2.6 eV makes this material suitable for bipolar magnetic switching and photocatalytic applications.