The effect of oxygen diffusion on the thermal decomposition kinetics of La[Fe(CN)6]·5H2O has been explored. In particular, the critical conditions under which LaFeO3 can be synthesized via solid-state combustion of this cyano complex precursor were analytically and numerically investigated. Thermal analysis experiments as well as simulations showed that the oxygen diffusion enhancement facilitates the formation of a self-propagating combustion front during the decomposition of La[Fe(CN)6]·5H2O. As a consequence, the sample undergoes local overheating that raises its temperature by several hundreds of degrees. This enables the production of LaFeO3 perovskite-type oxide with a minimum contribution of external heat resources. Although the self-propagating high-temperature method has already proven to be successful for the synthesis of perovskite-type oxides from cyano complex precursors under oxygen atmosphere, we will show that under the appropriate settings, air can be used instead. Moreover, the temperature of the front is related to the ease of oxygen diffusion. Therefore, the surface area and the crystal size of LaFeO3 perovskite-type powders obtained via solid state combustion have been controlled by controlling the gas flow rate at which the sample has been exposed during the treatment