This work demonstrates the effect of Sn, Cu, and Ag modification on the electrochemical performance and carbon tolerance of biogas-operated Ni/YSZ and Ni/ScCeSZ SOFC anodes. The tested cells were fabricated from commercial materials via aqueous tape casting method. A reverse co-casting technique was utilized to manufacture GDC-ScCeSZ-Ni/ScCeSZ half cells. An LSCF (La0.6Sr0.4Cr0.2Fe0.8O3) cathode was painted on the sintered half cells to ensure good performance at intermediate operating temperatures (700-800 °C). 1 wt% of Sn, Cu, and Ag (respect to Ni) were infiltrated into the anode scaffold and followed by calcination at different temperatures. Prepared cells were firstly tested at 700-800 °C in hydrogen fuel (H2:N2=3:1) for 24 h and then switched to simulated biogas (CH4:CO2:N2=2:1:1) for another 24 h. Electrochemical characterizations such as OCV, I-V, potentiostatic, galvanostatic, and electrochemical impedance spectroscopy were performed on each SOFC single cell. Scanning electron spectroscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and X-ray powder diffraction (XRD) were conducted to analyse the microstructure, surface elemental distribution, and electrochemical catalyst crystal structure of the prepared anodes, respectively.The obtained experimental results were compared with our previous work on 1 wt% Sn, Cu and Ag doped Ni/YSZ anodes. Carbon deposition on the modified Ni/YSZ anode surface was successfully suppressed after 24 h simulated biogas operation at 750 °C. Furthermore, the addition of a small amount of dopant significantly improved the electrochemical performance and long-term stability under dry methane reforming condition, especially for Sn and Ag-doped anodes. Cu agglomeration might occur at high operating temperature because of copper’s low melting point, resulting in unchanged cell performance under biogas operation. Therefore, the Cu-doped Ni/ScCeSZ/LSCF cells are expected achieve better cell performance at slightly reduced operating temperature.