CoFe2O4 prepared by sol-gel has been examined with respect to its catalytic performance for preferential CO oxidation in a H2-rich stream. In turn, the promoting effects of incorporation of Ce, Co, Cu, and Zr by impregnation on the surface of CoFe2O4 on the process are examined as well. The catalysts have been characterized by N2 adsorption, X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), temperature programmed reduction (TPR), and X-ray photoelectron spectra (XPS), as well as diffuse reflectance infrared DRIFTS under reaction conditions with the aim of establishing structure/activity relationships for the mentioned catalyst/process. It is shown that while the presence of the various metals on CoFe2O4 hinders a low temperature CO oxidation process, it appreciably enhances the activity above 125 °C. This is basically attributed to the surface modifications, i.e. cobalt oxidation, induced in CoFe2O4 upon introduction of the metals. In turn, no methanation activity is observed in any case except for the copper-containing catalyst, in which achievement of reduced states of cobalt appears most favored.