This paper is focused on the synthesis of ceria-doped Ni-ZrO2 nanocrystals (Ni-CZ) via a novel synthetic strategy based on wet impregnation and its application as anode material for solid oxide fuel cell (SOFC) directly fuelled by biogas. The electrochemical behaviour of Ni-CZ was evaluated by means of IV curves and impedance spectroscopy in H2 and simulated biogas at 750–850 °C using yttria stabilized zirconia (YSZ) electrolyte-supported cell. The cell achieved higher power density in H2 and at higher temperature. The distribution of relaxation time (DRT) analysis of impedance data was carried to determine the contribution of electrodes processes. Detailed of electrochemical analysis revealed that the cell performance limiting factor corresponds to the electrodes processes at low frequencies which are related to gas diffusion in H2 and dry reforming process and water-gas shit reaction coupled to gas diffusion in biogas. The cell showed a stable performance or even better activation in biogas under aggressive operation condition (400 mV) that could favour its degradation at 750 °C and 800 °C for 20 h and at 850 °C for 200 h. Furthermore post-tests analysis detected negligible carbon deposition on the anode surface. Although Ni-CZ could be postulated as SOFC anode material for direct biogas due to its good stability, an improvement its electrochemical perform is required.