The composites of Ni–Cu oxides with gadolinium doped ceria (GDC) are emerging as highly proficient anode catalysts, owing to their remarkable performance for solid oxide fuel cells operated with biogas. In this context, the nanocomposite catalysts (1 – x)NiO-xCuO/yGDC (x = 0.2–0.8; y = 1,1.3) are synthesized using a solid-state reaction route. The cubic and monoclinic structures are observed for NiO and CuO phases, respectively, while CeO2 showed cubic fluorite structure. The scanning electron microscopic images revealed a rise in the particle size with an increase in the copper and GDC concentration. The optical band gap values are calculated in the range 2.82–2.33 eV from UV–visible analysis. The Raman spectra confirmed the presence of vibration modes of CeO2 and NiO. The electrical conductivity of the nanocomposite anodes is increased as the concentration of copper and GDC increased and reached at 9.48 S cm–1 for 0.2NiO-0.8CuO/1.3GDC composition at 650 °C. The electrochemical performance of (1 – x)NiO-xCuO/yGDC (x = 0.2–0.8; y = 1,1.3)-based fuel cells is investigated with biogas fuel at 650 °C. Among all of the as-synthesized anodes, the fuel cell with composition 0.2NiO-0.8CuO/1.3GDC showed the best performance, such as an open circuit voltage of 0.84 V and peak power density of 72 mW cm–2. However, from these findings, it can be inferred that among all other compositions, the 0.2NiO-0.8CuO/1.3GDC anode is a superior combination for the high electrochemical performance of solid oxide fuel cells fueled with biogas.