The development of active catalysts is always challenging in the field of energy devices. In this work, Li-doped, Ni−Cu-based, and Ni-free nanocomposite anode catalysts are synthesized and studied for solid-oxide fuel cells (SOFCs) operated at a low temperature using hydrogen and biogas as fuels. The catalysts with compositions Ni 0.6 Li 0.2 Cu 0.2 -oxide/ La 0 . 2 Ce 0 . 8 O 2δ (NLC622-LDC), Ni 0 . 2 Li 0 . 2 Cu 0 . 6 -oxide/ La 0.2 Ce 0.8 O 2-δ (NLC226-LDC), and Ni 0.0 Li 0.2 Cu 0.8 -oxide/ La 0.2 Ce 0.8 O 2-δ (NLC028-LDC) are synthesized using the glycerol-assisted gel combustion route (GGCR). The structural analysis revealed the cubic structure of metallic oxide materials such as NiO and CuO phases while the cubic fluorite structure of CeO 2 as an ionic oxide phase. The optical band gaps (E g 's) of anode catalysts NLC622-LDC, NLC226-LDC, and NLC028-LDC are found to be 2.08, 2.29, and 2.37 eV, respectively. Furthermore, the anode catalyst with a higher nickel concentration shows better electrical conductivity and a lower activation energy of 3.47 S cm −1 and 0.67 eV at 600 °C, respectively, as compared to those of a nickel-free anode catalyst with lower nickel content. The electrochemical behavior of nanocomposites is studied at 600 °C using Nyquist plots. Electrochemical impedance analysis is carried out to see the effect of hydrocarbon fuel like biogas at the anode side. Finally, the electrochemical performance of NiLiCu-LDC catalyst-based fuel cells is tested under hydrogen and biogas fuels. Overall, the fuel cell based on the NLC622-LDC anode catalyst has higher OCV and power density with both fuels, hydrogen and biogas. Therefore, NLC622-LDC is a highly catalytically active anode catalyst which demonstrated significantly better performance for SOFCs operated at a low temperature (500−600 °C) without any carbon resistance.