High porosity Co-Al-Fe intermetallic with 3D-microstructures were one-step synthesized via a novel thermal explosion reaction. A link between pore structure and permeability was established using 3D-XRM technology. The corrosion resistance of the samples with different Fe contents was investigated at 900 °C under an oxygen/sulphur atmosphere for up to 120 h. The results showed that the pore structure of the samples remains stable, and the internal matrices are intact due to the formation of a thin protective layer of Al2O3 and Fe2O3 on the surface of the product skeleton. In addition, inward diffusion of S leads to the formation of FeS nodules.