Rod-shaped CeCoaOx catalysts with varying Co doping ratios (a = 0.012, 0.017, 0.022) were synthesized by calcinating the Ce-MOF, prepared using a water bath and trimesic acid as an organic ligand. This method ensured a high degree of elemental mixing, abundant pore channels and a large specific surface area are all beneficial for enhancing toluene catalytic oxidation activity. Raman, XPS, and catalytic activity tests confirmed strong interactions between the Ce and Co oxides, promoting the formation of more Ce3+ and oxygen vacancies. Among these catalysts, CeCo0.012Ox exhibited superior catalytic performance for toluene oxidation under weight hourly space velocity of 40,000 mL·g−1·h−1. The temperature at toluene conversion of 10 %, 50 % and 90 % was 140, 205 and 226 °C, respectively, which was 61, 12 and 14 °C higher than those over pure phase CeO2. CeCo0.012Ox also demonstrated excellent activity stability under high humidity (10 vol%H2O). H2-TPR, O2-TPD and in situ DRIFTS also revealed that surface-absorbed oxygen species played a crucial role in catalytic activity, with CeCo0.012Ox benefiting from abundant oxygen vacancies and effective oxygen species mobility.