The combustion of metal fuels as energy carriers in a closed-cycle carbon-free process is a promising approach for reducing CO₂ emissions in the energy sector. For a possible large-scale implementation, the influence of process conditions on particle properties and vice versa has to be well understood. In this study, the influence of different fuel–air equivalence ratios on particle morphology, size and degree of oxidation in an iron–air model burner is investigated by means of small- and wide-angle X-ray scattering, laser diffraction analysis and electron microscopy. The results show a decrease in median particle size and an increase in the degree of oxidation for leaner combustion conditions. The difference of 1.94 μm in median particle size between lean and rich conditions is twentyfold greater than the expected amount and can be connected to an increased intensity of microexplosions and nanoparticle formation for oxygen-rich atmospheres. Furthermore, the influence of the process conditions on the fuel usage efficiency is investigated, yielding efficiencies of up to 0.93. Furthermore, by choosing a suitable particle size range of 1 to 10 μm, the amount of residual iron content can be minimized. The results emphasize that particle size plays a key role in optimizing this process for the future.