New catalysts designed as glass crystal microspheres were studied by XPS, SEM, XRD and Mossbauer spectroscopy. The data obtained indicated that after treatment of catalysts with HF the fluorination of lattice took place leading to stabilization of Fe3O4 phase. The catalytic activity of initial catalysts and catalysts already treated with HF in the reactions of deep oxidation and oxidative coupling of methane was determined. The yield of C-2-products at 1123 K was 16% for oxyfluoride systems using the gas mixture CH4:O-2=85:15 vol%.