Synthesis gas production via selective oxidation of methane at 600 degrees C in a pulse reaction over La-0.75 Sr-0.25 (Fe-0.8 Co-0.2)(1-x) GaxO3-delta (X = 0.1, 0.25, 0.4) perovskite-supported rhodium catalysts, was investigated. The perovskite oxides were prepared by sol-gel citrate method and characterized by X-ray Diffraction (XRD), Moessbauer Spectroscopy (MS), Temperature Programmed Reduction (TPR-H2), Xray Photoelectron Spectroscopy (XPS) and High Resolution Transmission Electron Microscopy (HRTEM). According to XRD analysis, the synthesized samples were a single perovskite phase. The perovskite structure of Ga substituted samples remained stable after TPR-H2, as confirmed by XRD. Data of MS identified Fe3+ ions in two distinctive coordination environments, and Fe4+ ions. The Rh2O3 thin overlayer was detected by the HRTEM for the Rh impregnated perovskite oxides. During the interaction of methane with oxidized perovskite-supported Rh (0.5 wt.%) catalysts, besides CO, H-2, and surface carbon, CO2 and H2O were formed. The Rh perovskite catalyst with x = 0.25 gallium exhibits the highest catalytic activity of 83% at 600 degrees C. The CO selectivity was affected by the reducibility of La-0.75 Sr-0.25 (Fe-0.8 Co-0.2)(1-x) GaxO3-delta perovskite materials. (C) 2015 Elsevier B.V. All rights reserved.