This work reports how a novel macro-porous silica foam thin layer, applicable as a new catalyst support with high porosity, can be produced via spheres templating method. Three-dimensional close-packed crystals of polystyrene (PS) spheres were assembled on a porous alumina disk via vacuum filtration. The PS templates were filled with a silica colloidal solution, after annealing and adsorption of a surfactant, to generate interconnected macropores after calcination.