Previous work on calcium ferrites showed they were able to convert syngas to hydrogen via chemical looping. The mixture of iron and calcium and their oxides has different thermodynamic properties than iron oxide alone. Here, the use of methane, an abundant fuel, is investigated as the reductant in chemical looping syngas production. In contrast to syngas-fueled cycles, the looping materials became more active with cycling using methane as the fuel. When reduced by methane, the looping material often showed a significant induction period, indicating that products of reduction (in particular metallic Fe) acted as a catalyst for further reduction. The behavior in a thermogravimetric analyzer (TGA) and a fluidized bed was comparable, i.e., no degradation with cycling. The reduced C2F appeared to be easily reformed when oxidized with CO2, and there was little evidence of bulk phase segregation. The improved kinetics on cycling was likely due to the separation of metallic Fe onto the surface. Using hydrogen to partially reduce C2F promotes the catalytic pyrolysis of methane.