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Ni-free solid oxide fuel cell ceramic anode consisting of Ruddlesden–Popper type layered perovskite (Pr_0.4Sr_0.6)₃(Fe_0.85Nb_0.15)₂O₇ (RP-PSFN) matrix with homogenously dispersed CoFe bi-metallic alloy (CFA) nanoparticles has been fabricated by in situ annealing the porous perovskite Pr_0.4Sr_0.6Co_0.2Fe_0.7Nb_0.1O_3−δ membrane in H₂ at 900 °C. The RP-PCFN-CFA ceramic anode has demonstrated a similar catalytic activity to Ni-based ceramic anode. La_0.8Sr_0.2Ga_0.83Mg_0.17O_3−δ electrolyte supported SOFC single cell with RP-PSFN-CFA anode generates maximum power outputs of 0.59 and 0.92 W cm⁻² in wet C₃H₈ (3 vol% H₂O) at 800 and 850 °C, respectively. Moreover, the single cell shows a stable power output under a constant current load of 0.40 A cm⁻² in wet C₃H₈ at 800 °C, indicating an excellent coking resistance.