The escalating global demand for energy, coupled with growing environmental concerns, has intensified efforts to develop sustainable and diversified energy solutions. Among various energy conversion devices, solid oxide fuel cells (SOFCs) have garnered significant attention due to their exceptional energy conversion efficiency and ability to utilize hydrocarbon fuels directly. However, conventional SOFC anodes based on Ni/YSZ cermets suffer from critical drawbacks such as carbon deposition and sulfur poisoning when operated with hydrocarbon fuels. To address these limitations, mixed ionic and electronic conducting (MIEC) materials, notably La0.2Sr0.8Ti0.9Ni0.1O3 (LSTN), have emerged as promising alternatives due to their superior carbon and sulfur tolerance, alongside robust thermal and redox stability. This study investigates the electro-oxidation of methanol over a composite anode consisting of LSTN integrated with samarium-doped ceria (SDC). To enhance the electrochemical performance, LaFe0.6Co0.4O3 (LFC) precursor solutions of varying concentrations were impregnated into the composite structure. Impedance spectroscopy results demonstrated that LFC incorporation, particularly when synthesized with ethylene glycol (EG), markedly reduced electrode polarization resistance and improved catalytic activity. X-ray diffraction analysis further confirmed the successful formation of the LFC perovskite phase within the porous anode framework. These findings underscore that LFC-impregnated LSTN/SDC composite anodes, especially those synthesized with EG, significantly enhance the methanol electro-oxidation process, establishing them as strong candidates for high-performance SOFC applications. Overall, this research contributes to advancing the efficiency and durability of solid oxide fuel cells, thereby supporting the transition toward sustainable energy technologies.