<p>Developing advanced methane conversion catalysts is essential for reducing methane emissions and enhancing gas turbine performance. In this study, LaFeO₃ perovskite catalysts supported on high-surface-area γ-Al₂O₃ and MgAl₂O₄ were synthesized via the sol-gel method and evaluated for methane oxidation. Structural and compositional analyses confirmed the successful incorporation of LaFeO₃ on MgAl₂O₄, whereas its formation on γ-Al₂O₃ was limited by interactions with underlying support, leading to secondary phase formation. Quantitative modeling based on rate equations revealed the contributions of two oxygen species (i.e., surface oxygen and lattice oxygen) to the reaction, elucidating catalyst-specific reaction pathways. The MgAl₂O₄-supported LaFeO₃ exhibited enhanced methane oxidation performance compared to conventional LaFeO₃ due to the increased participation of both lattice and surface oxygen species in the reaction. In contrast, the γ-Al₂O₃-supported LaFeO₃ catalyst performed similarly to bulk LaFeO₃, likely due to Al-induced secondary phases that suppressed oxygen availability. These findings offer novel insights into optimizing methane oxidation catalysts through rational material design.</p> Graphical Abstract <p></p>