Perovskite oxides of the type of LaxCa1-xMyAl1-yO3-delta (M = Co, Cr, Fe, Mn; x = 0.5; y = 0.7-1.0) were prepared using the polymerization methods and evaluated via N-2 adsorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), energy dispersive X-ray (EDX) spectroscopy, temperature-programmed reduction by hydrogen (TPR-H-2) and temperature-programmed oxidation by oxygen (TPO-O-2). Catalytic behaviour of the perovskite oxides during methane oxidation was studied using a tubular fixed-bed reactor. In a partial oxidation, which proceeded in two steps, there was total oxidation in the first step and CO2 and H2O were formed; in the second step, the total oxidation products oxidized methane by (dry and wet) reforming reactions to yield CO and H-2. Total oxidation and the two reforming reactions proceeded on two types of an active centre formed by transition metal ions, oxygen vacancies and oxide ions. The catalytic system La-Ca-Co-Al-O which contained aluminium, decomposed in partial oxidation of methane (POM) into a composite that contained firmly bonded cobalt nanoparticles in the surface of a substrate made up of La2O3, CaO and Al2O3 which catalysed POM with a high methane conversion and hydrogen selectivity. (C) 2017 Published by Elsevier Ltd on behalf of Hydrogen Energy Publications LLC.