In the present study, La1 − xCrxFeO3 (x = 0.0, 0.3, 0.6, 0.9, 1.0) was synthesized by micro-emulsion route and characterized by X-ray Diffraction (XRD), Fourier Transform Infrared (FTIR), Scanning electron microscope (SEM), Energy-dispersive X-ray (EDX) techniques. The dielectric, ferroelectric and photocatalytic properties were investigated and compared with un-doped material. The XRD analysis revealed orthorhombic geometry of La1 − xCrxFeO3 (x = 0.0, 0.3, 0.6, 0.9, 1.0), Cr was doped successfully into the lattice structure of LaFeO3 and particles were spherical and in agglomerated form. The grain sizes were recorded to be 15, 16.9, 17.1, 17.65 and 18.3 (nm) for La1 − xCrxFeO3 (x = 0.0, 0.3, 0.6, 0.9, 1.0), respectively. EDX analysis confirmed the purity of LaCrFeO3 samples. The lattice parameters, bulk density, X-ray density, crystalline size and porosity were determined were also determined of all the La1 − xCrxFeO3 samples. The dielectric constant and dielectric loss values decreased at higher frequency and Cr concentration affected the dielectric properties. The photocatalytic activity (PCA) was evaluated by degrading Congo Red (CR) dye under solar light irradiation and up to 85.43% dye degradation was achieved within 45 min of irradiation. Phyto-toxicity analysis before and after dye degradation was performed, which revealed the toxicity reduction in response of dye degradation. Results revealed that lanthanum ferrite (perovskite) doping with Cr could possibly be employed to enhance the ferroelectric, dielectric and photocatalytic properties.