Abstract Cobalt ferrite was obtained by the thermolysis of two new cobalt ferrioxalate coordination compounds, namely [Fe2Co(C2O4)3(OH)2(OH2)4]·2H2O (I) and [Fe2Co(C2O4)4(OH2)6] (II). The precursors were characterized by chemical analysis, electronic and vibrational spectra and thermal analysis. The corresponding oxides obtained after a heating treatment of the precursors at 350 °C/h were extensively investigated by various methods such as XRD, IR, SEM, TEM coupled with EDX, TPR, Mössbauer spectroscopy, magnetic investigations and N2 adsorption–desorption isotherms. The mesoporous oxides, consisting of homogeneous particles as shape and size with mean crystallites size values of 111 (I) and 86 (II) Å, exhibit high surface areas (77.6 (I) and 55.7 (II) m2 g−1). The cobalt ferrites’ catalytic performances for methane combustion are close to that of a platinum-based catalyst, the catalytic activity being analyzed and interpreted considering ferrites distinctive properties.