Shape evolution of nanostructured LaFeO₃ with fascinating morphologies like cubes, rods and spheres was successfully synthesized by a facile and environmentally friendly hydrothermal process. Tuning the morphologies was achieved using different surfactants. The prepared samples were systematically characterized using X-ray diffraction, micro-Raman spectroscopy, scanning electron microscopy and high-resolution transmission electron microscopy for structural, morphological and chemical composition analysis by X-ray photoelectron spectroscopy. The optical properties of prepared samples were studied employing UV-Vis diffusion reflectance analysis. Brunauer–Emmett–Teller measurement reveals a large surface area for all the prepared nanostructures. Most importantly, the visible-light photocatalytic activities of the three LaFeO₃ nanostructures were evaluated by photocatalytic decolorization of Rhodamine B in aqueous solution. The enhanced photocatalytic activity of LaFeO₃ nanospheres compared to other nanostructures and commercial Degussa P25 TiO₂ can be ascribed to high specific surface area, pore size distribution and the smaller particle size. The underlying growth mechanism responsible for the formation of LaFeO₃ nanostructures is also discussed. The results from this study illustrate the morphology-dependent photocatalytic performance of LaFeO₃.