Composite catalysts containing various forms of metallic or oxide iron ((Fe0 or FexOy, Fe3+) in combination with an inert matrix (γ-Al2O3) were obtained and their catalytic ability in the propane cracking reaction was studied. It is shown that for pure aluminum oxide, no catalytic effect is observed in this reaction. The synthesis methods implemented in this work allowed us to obtain various catalytic centers that can effectively carry out electron transfer by changing the degree of iron oxidation during the transformation of the initial substances into the target reaction products. It is proved that the use of iron nano-particles for formation of catalytic centers does not lead to a noticeable improvement in the technological yield of propylene compared to the Fe3+/Al2O3 material. Use of an inert oxide substrate (γ-Al2O3) and various iron compounds makes it possible to create a bifunctional catalytic center containing Fe(III) and Al(III) ions, which provides an energetically favorable interaction with the propane molecule and further breaking of the strongest C-H bond at a primary carbon atom. The synthesized catalytic systems can be used for thermocatalytic processes in natural gas processing instead of catalysts based on noble metals.