The bulk-phase Cu-Ce-Zr catalyst BP-gel was prepared by the sol-gel method and investigated for the oxidation of toluene in a fixed-bed reactor. For comparison, other bulk-phase catalysts (thermal decomposition (BP-td), solid-state reaction (BP-sr)) and supported catalysts (incipient wetness impregnation (S-iwi), saturated impregnation (S-si)) were tested. The results showed that the catalytic activities were in the following order: BP-gel>S-si>S-iwi>BP-td>BP-sr. The BP-gel catalyst, which has a mesoporous structure, is beneficial for the mass transfer of reactant molecules. The thermal stability of the BP-gel catalyst was improved by the introduction of ZrO2. Bulk CuO in the catalysts reduced their activity because the synergetic effect between CuO and CeO2 decreased. The low-temperature reducibility, large pore sizes, rich oxygen vacancies, and active oxygen species contributed to the highest activity of the BP-gel, with a T-90 as low as 219 degrees C, and no deactivation was observed during the 72 h stability test at the set temperature.