The design of perovskite oxides with improved textural properties in combination with tunable composition variations is a forward-looking strategy for the preparation of next generation catalytic converter. In the present work we report the template-free synthesis of mesoporous solid solutions of La0.3Sr0.7Ti1-xFexO3 +/-delta (0 5 <= x <= 0.5) and the study of their catalytic performance towards CH4 and CO oxidation. Using an innovative polymer complex route, phase pure perovskite solid solutions with specific surface area of 65 m(2) g(-1) and average pore size of 15 nm were prepared. The iron concentration increase led to a progressive enhancement of not only both concentration and transport of the charge carriers but also reducibility and oxygen desorption capability on the catalyst. As a result, we observed almost complete conversion of CH4 and CO at 600 degrees C and 300 degrees C, respectively. Kinetic studies on methane oxidation showed that competing suprafacial and intrafacial reaction mechanisms coexist, and that the concentration of 30% of Fe maximizes the suprafacial contribution. Under reducing conditions at 600 degrees C the materials retained their structural and morphological integrity, showing superior stability. Finally, the reaction rate of CH4 and CO conversion evidenced that our systems are by a maximum of 90 times more performing than other bulk and nanoporous Fe-based perovskites in literature (e.g. La-0.66-Sr0.34C0.2Fe0.8O3-delta), as a result their large surface area, intimate gas solid contact and short intragrain oxygen diffusion pathways induced by the mesoporous structure.