Porous Ni, Ni-Co, Ni-Fe, and Ni-Cu magnetic alloys with a morphology similar to a giant barrel sponge were synthesized via a facile co-precipitation procedure and then by hydrogen reduction treatment. For the first time, the non-supported alloys with their unique morphology were employed in catalytic biogas decomposition (CBD) at a reaction temperature of 700 °C and 100 mL min-1 to produce syngas and carbon bio-nanofilaments, and the catalysts' behavior, CH₄ and CO₂ conversion, and the carbon produced during the reaction were investigated. All of the equimolar alloy catalysts showed good activity and stability for the catalytic biogas decomposition. The highest sustainability factor (0.66) and carbon yield (424%) were accomplished with the Ni-Co alloy without any significant inactivation for six hours, while the highest carbon efficiency of 36.43 was obtained with the Ni-Co catalyst, which is considered relatively low in comparison with industry standards, indicating a low carbon production process efficiency, possibly due to the relatively high biogas flow rate. The higher activity of the Ni-Co alloy catalyst was associated with the synergistic impact between nickel and cobalt, allowing the catalyst to maintain a high stability throughout the reaction period. Moreover, highly uniform, interwoven carbon bio-nanofilaments with a parallel and fishbone structure were achieved.