Macroporous synthetic opal grown from non-porous silica nanoparticles and decorated by Co and Ce oxides was applied for the catalytic CO oxidation in the inert (TOX) and H2-rich (PROX) gas mixtures. Prepared materials were studied by methods of SEM, TEM, EDX, XRD, XPS and FTIR spectroscopy. The relationship between synthesis conditions, structure, and catalytic behavior of composites is discussed. The best Co-O-Ce interaction and the highest activity in the CO-TOX and PROX are achieved when cerium oxide was added prior to the addition of cobalt oxide. In this case highly dispersed particles of Co3O4 and CeO2 are located in close proximity on the silica surface and anchored between the opal spheres. The use of Co/Ce decorated synthetic opal as a nanoreactor for the catalytic oxidation of CO in the H2 excess makes it possible to achieve 99.5 % conversion of CO at 150°C, the high efficiency and selectivity of the process are maintained in multiple cyclic tests in heating and cooling modes. The synergistic activity of Co and Ce oxides was observed when they both were located together on the outer surface of non-porous SiO2 nanospheres. These results are superior to known data for other catalysts based on Co and Ce oxides.