We develop synthesis routes for materials with hierarchical porosity in the scales of the nm (mesoscale) to the submicrometer (macroscale), processed as colloids, thin films, or monoliths, by combining sol-gel synthesis, self-assembly, controlled phase separation, selective functionalisation and pattern transfer. In this way, we can generate Nanosystems (thin films or core-shell colloids), multiple pore size multilayers (multiscale), in which a variety of organic functions can be located in certain parts of the space (multifunction). The knowledge generated is useful for applications in advanced coatings with innovative physical and chemical features: optical materials, nanoelectronics, chem-selective materials, "lab-on-chip", or biomaterials.