Novel meso-/macroporous SiO2 monoliths have been reached by applying a nanotectonic pathway within a confined geometry, i.e. a non-static air-liquid foam patterning process. Final scaffolds are a very close transcription of the tailored periodic air-liquid foam template while coalesced silica particles are texturing the as-synthesized foam walls. The interconnected nanoparticles and associated void space between adjacent particles allow generating intrinsic mesopores, thereby defining hierarchically organized porous scaffolds. The good control over both the air-liquid foam’s water volume fraction and the bubble size allow a rational tuning of the macropore shape (diameter, Plateau border’s width). In contrast with previous study, closed-cell structures can be reached, while the opal like scaffold structure is maintained with thermal treatment, avoiding thus strong shrinkage associated to the sintering effect.