In this work, a correlation between ceria loading (0, 2, 5, 10, 20, 50 wt%) in Pt/Al2O3-CeO2 catalysts with the catalytic activity of 1-butanol and toluene oxidation is presented. The materials were characterized by TPR, CO chemisorption and TEM; additionally, the capacity to store/release oxygen was determined with the OBC technique in a transient state. The interaction of the CeO2 species with the active phase was obtained by TPR experiments, which were complemented with CO chemisorption and TEM analyses, to understand the SMSI effect and Pt dispersion in the different catalysts. A complex relation between SMSI, Pt particle size and the capacity to store/release oxygen with the activity in VOC oxidation was found. It is concluded that using Pt/Al2O3–CeO2 in deep oxidation of 1-butanol and toluene, the light-off temperature (50% conversion) is reduced with higher values of OBC and Pt dispersion, but to reach 100% of toluene removal, it is necessary to have lower SMSI effect and lower Pt dispersion. The results show that the best catalytic performance, for 50 and 100% conversion, was obtained with the material with 5% CeO2.