CH4 temperature programmed surface reaction (TPSR) and CH4 oxy-CO2 TPSR are applied to test Ni (10Ni), Co (10Co) and Co–Ni (5Co5Ni) aerogel catalysts in the CH4 oxy-CO2 reforming reaction. Monometallic 10Ni outperforms 10Co and bimetallic 5Co5Ni aerogel catalysts in the CH4-TPSR test. The CH4 activation temperature (AT) of 10Ni and 5Co5Ni is 160 °C lower than that of 10Co, indicating that CH4 can be activated more effectively on 10Ni and 5Co5Ni. As a result, the critical temperature (CT) of 10Ni and 5Co5Ni in the CH4 oxy-CO2 TPSR test are 680 °C and 695 °C, whereas 10Co shows no CT in the test. The CH4 oxy-CO2 TPSR test also reveals that although CTs of the catalyst are independent of the reduction pretreatment, the catalytic oxidation abilities for carbon species are greatly promoted after reduction. The calcined samples activate CH4 via the combination of combustion and partial oxidation, while the reduced sample activate CH4 mainly via combustion. Furthermore, the reduced 5Co5Ni activates and completes CH4 oxidation at temperatures 60 °C and 128 °C lower than those of 10Ni, suggesting its higher ability to catalyze the oxidation of carbon species generated in CH4 reforming, which could be account for its better performance than those of the monometallic catalysts.