Sodium-tungsten-manganese supported on silica (Na-W-Mn/SiO2) and hydroxyapatite (HAp) are representative catalysts for oxidative coupling of methane (OCM). In this work, the effect of the HAp doping in a Na-WMn/ SiO2 catalysts on the OCM performance was studied. To enhance the ethylene selectivity of the Na-W-Mn/SiO2 catalyst, silica supports were coated with HAp containing hydroxyl and phosphate groups as oxygen species. A series of Na-W-Mn/xHAp_SiO2 (x=1, 3, 5 and 7) catalysts with the different HAp coating cycles were prepared through the alternative soaking method, and X-ray diffraction (XRD) and scanning electron microscopy (SEM) showed that the amount of HAp doping was dependent on the HAp coating cycles. In addition, the change of oxygen species upon HAp doping was examined with X-ray photoelectron spectroscopy (XPS) and oxygen temperature-programmed desorption (O2-TPD) techniques. With HAp doping, the increase of oxygen species assigned to metal oxide responsible for selective oxidation of methane to ethylene was observed in O 1s XPS spectra. In addition, weakly bound oxygen species were observed with the introduction of HAp doping in O2-TPD profiles of prepared catalysts. The influence of these oxygen species on OCM catalytic performance was evaluated at an operating temperature of 775 oC and gas hourly space velocity of 18,000ml/gcat.h. The amount of HAp doping provided reactive oxygen species for oxidative dehydrogenation of ethane, which resulted in as much as 120% increase in C2H4/C2H6 ratio over the Na-W-Mn/ 3HAp_SiO2 catalyst compared to the Na-W-Mn/SiO2 catalyst.