In the present study, we successfully synthesized LaVxFe1−xO3 powders following a standard sol-gel protocol under ambient air conditions. This synthesis was made possible thanks to the use of ascorbic acid as a reducing agent. There was no need for a controlled environment or vacuum to prevent vanadium from oxidation. Ascorbic acid has the advantage of helping to adjust the pH of the solution until it turns green, which is an indication of the presence of the V+3 oxidation state. Structural characterization was performed using X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, and Fourier transform infrared spectroscopy, while optical bandgap energies were determined using UV-Visible spectrophotometry. The vanadium fraction of 25% vanadium showed tiny, agglomerated nanoparticles with an estimated size of about 30 nm, and a globally orthorhombic structure was obtained. Deeper infrared analyzes were able to highlight a deformed structure of LaFeO3 inside which very few FeO6 octahedra are replaced by deformed VO6 octahedra. Due to these, a bandgap reduction occurred from 2.31 eV to 1.86 eV, proving that the combination of lanthanum ferrite and lanthanum vanadate is a successful strategy to tune the bandgap energy while retaining the orthorhombic structure. Such a combination therefore offers a promising way for the fabrication of devices with a high potential for harvesting and conversion for applications based on solar irradiation.