The oxidation of methane with nitrous oxide on PO4-deficient barium hydroxyapatite (BaHAp) has been investigated in the presence and absence of tetrachloromethane (TCM) and compared to that with oxygen in order to obtain possible activities for the partial oxidation of methane using hydroxyapatite catalysts. In the absence of an external oxidant, the addition of TCM suppressed the formation of oxidation products with the essential elimination of CO and CO2, in favor of an increased selectivity to C2H6 while that to C2H4 changed relatively Little, indicating that TCM directly contributes to an activation of structural oxygen of the catalyst. In the absence of TCM and with nitrous oxide as the oxidant, the maximum selectivity to the coupling products reached approximately 80% at a conversion of methane of 4.5% at 0.5 h on-stream although calcium hydroxyapatites mainly afforded CO, under the corresponding conditions. However, carbon oxides, primarily CO2, were the predominant products with oxygen. With nitrous oxide and in the presence of TCM with increasing time-on-stream carbon monoxide became the only significant product. The formation of barium chlorapatite is demonstrated and the relative effects of nitrous oxide and TCM are compared.