Monosodium zirconium phosphate or disodium zirconium phosphate by itself did not catalyze the oxidative coupling of methane and also the deep oxidation of methane. However, NaCl-added sodium zirconium phosphates showed markedly increased activity and high C₂₊ selectivity in the oxidative coupling of methane, which indicates that chlorine species or NaCl plays an essential role in the catalytic action. The catalytic performance became more stable with increasing content of NaCl. The primary reason for the catalyst deactivation is the loss of chlorine, and a possible secondary reason is the transformation of catalytic substance to the sodium zirconium phosphates having higher Na/Zr ratios or decomposition of sodium zirconium phosphates to zirconium oxide and sodium phosphate. Two kinds of surface chlorine species were observed, and the lower-binding-energy species is considered to be much more active than the higher-binding-energy species in methane activation, although the latter is present in a larger amount than the former.