Via integrative chemistry, the first CoOx−SiO 2 (HIPE) self-standing monoliths of cobalt nano-oxides embedded within silica macro−mesocellular hosts have been prepared. These binary CoOx−SiO 2 porous nanostructure (MUB-100(x)) materials present an average of 95% porosity. We found out that high cobalt concentration maintains the hexagonal-2D organization of the mesoscopic voids when applying the thermal treatment at 700 °C. Their specific surface areas fall between 400 and 500 m 2 g −1 when assessed by Ar physisorption measurements. At the microscopic length scale, as revealed through magnetic investigations, the low cobalt content foams MUB-100(1) and MUB-100(2) are made of the amorphous β-Co(OH) 2 phase coexisting with the silica network, whereas increasing the cobalt concentration during the one-pot syntheses (MUB-100(3) and MUB-(4) materials) favors the formation of the spinel Co 3 O 4 and olivine Co 2 SiO 4 crystalline nanoparticles embedded within silica. When considering the CO oxidation catalytic performance, the MUB-100(4) is able to totally convert the CO flow before 200 °C (starting at 125 °C) while achieving 50% conversion for a light-off temperature (T 50) of 145 °C, revealing the good efficiency of the MUB-100(4) in CO oxidation with which up to 4 catalytic cycles have been performed without disrupting drastically the catalytic performance and reaching thermodynamic stability from cycle 2 to cycle 4.