A series of monolithic Ni/CeO_2-ZrO_2/γ-Al_2O_3 catalysts for the POM reaction were prepared. The activity test shows that the catalyst has the best performance when CeO_2-ZrO_2 content is 8 wt%.The synergistic actions between CeO_2-ZrO_2 and γ-Al_2O_3 improve highly catalytic activity by increasing CH_4 conversion, H_2 and CO selectivity. XPS analysis of the used catalyst indicates that there coexist Ce~(4+) and Ce~(3+). A series of monolithic Ni / CeO_2-ZrO_2 / γ-Al_2O_3 catalysts for the POM reaction were prepared. The activity test shows that the catalyst has the best performance when CeO_2-ZrO_2 content is 8 wt%. The synergistic actions between CeO_2-ZrO_2 and γ-Al 2 O 3 improves the catalytic activity by increasing CH_4 conversion, H_2 and CO selectivity. XPS analysis of the used catalyst indicates that there is coexist Ce ~ (4+) and Ce ~ (3+).