We studied the oxidative coupling of methane over the LaF3/La2O3 (50 : 50) catalyst. The catalyst was found active even at 873 K. At 1023 K, the C2 yield was 12.7% at 26.0% CH4 conversion and 49.1% C2 selectivity. It was found to be stable and had a lifetime not less than 50 h at 1023 K. The catalyst was effective in C2H6 conversion to C2H4. XRD results indicated that the catalyst was mainly rhombohedral LaOF. It is suggested that the catalyst has ample stoichiometric defects and generates active oxygen sites suitable for methane dehydrogenation.