The multi-component catalysts we prepared exhibited high performance for the oxidative coupling of methane. The highest activity of catalysts was obtained over the Na-W-Mn-Zr-S-P/SiO2 at the temperature of 1,023 K, on which the C-2 yield was 23.5% at the methane conversion of 43.8%. XRD and XPS results showed the S, P addition could lead to the increase of lattice oxygen concentration and the formation of phase such as Na2SO4, Na2Zr(PO4)(2) on the catalysts. These phases play great roles in activity of the catalysts system.