In this work, we describe the effects of thermal treatments on the structural, morphological, and textural properties of nanocomposites formed by nickel ferrite dispersed in xerogel and aerogel silica matrices. The catalytic properties for the total oxidation of an organochloro model contaminant, the chlorobenzene, are also evaluated. Wet samples with different amounts of NiFe2O4 in matrix were prepared by sol–gel process. Xerogels and aerogels obtained in monolithic form were prepared by controlled and hypercritical drying, respectively, and heated at temperatures between 300 and 1,100°C. The specific surface area and total pore volume of the samples change with heating mainly due to the variation on their texture. The xerogel treated at 500°C and the aerogel treated at 700°C showed the most catalytic activity, converting chlorobenzene at temperatures as low as 150°C, while the other catalysts were active only at temperatures higher than 300°C. No organic by-products were observed in the oxidation of chlorobenzene, suggesting that total oxidation takes place under the reaction conditions. A strong decrease in catalytic activity was observed for nanocomposites treated at 1,100°C, due to matrix densification, which led to the encapsulation of the ferrite particles and hindered the access of the gas to the ferrite surface.