Single-phase nanocrystalline 4CaO·Al2O3·Fe2O3 powders were prepared directly from the combustion reaction using a new cost-effective, time-saving, and environmentally friendly version of solution combustion synthesis. Instead of a single fuel, a fuel mixture of urea and β-alanine was used. It was shown by x-ray diffraction, energy-dispersive x-ray analysis, thermogravimetric analysis, and optical microscopy that this new version of the solution combustion synthesis allows the maximization of the exothermic effect associated with the combustion reaction. On the other hand, it was shown that the traditional version of combustion synthesis involving the use of a single fuel, such as urea or β-alanine, does not ensure the formation of Ca4Al2Fe2O10 unless subsequent thermal treatments are applied. It was suggested that the occurrence of combustion reactions cannot be regarded only in terms of adiabatic temperature, as the kinetic aspects overrule the thermodynamic ones.