Chemical looping combustion is a clean combustion technology for fossil or renewable fuels. In a previous demonstration, chemical looping was applied to CO2 activation via reduction to CO with concurrent production of synthesis gas (CO + H2) from CH4 via rationally designed Fe‐Ni alloys. Here, it is demonstrated that that a simple physical mixture can even outperform the equivalent alloy based on an intricate gas phase mediated coupling between the two metals: Ni cracks methane to carbon and H2. The latter then reduces iron oxide carrier, forming steam, which gasifies the carbon deposits on Ni to produce a mixture of CO + H2, thus regenerating the active Ni surface. It was suggested that the principle demonstrated here—the gas phase‐mediated coupling of two solid reactants with distinct functionalities—should be applicable broadly toward oxidation reactions and hence opens a new avenue for rational design of chemical looping processes. © 2016 American Institute of Chemical Engineers AIChE J, 63: 51–59, 2017