In this paper, we will thoroughly review a novel and versatile self-formation phenomenon that can be exploited to target porous hierarchies of materials without need of any external templates only on the basis of the chemistry of metal alkoxides and alkylmetals. These hierarchically porous materials have unique structures, which are made of either parallel funnel-like/straight macrochannels or 3D continuous interconnected macroporous foams with micro/mesoporous walls. The self-generated porogen mechanism has been proposed, leading to a series of techniques to tailor porous hierarchy, i.e. the use of different chemical precursors (single metal alkoxides, mixed metal alkoxides, single molecular precursors with two different alkoxide functionalities, alkylmetals, etc., …), the control of their hydrolysis and condensation rates (pH, chelating agents,…) and the addition of alkoxysilanes as co-reactant. Various chemical compositions from single or binary metal oxides, to aluminosilicates, aluminophosphates, silicoaluminophosphates, metallophosphates,… can be prepared, offering a panel of potential applications. Some perspectives have been proposed to transform the synthesized materials with a hierarchy of pore sizes to micro–meso–macroporous crystalline materials with zeolite architectures. The advantages of this self-formation preparation method have been discussed compared to traditional templating methods. The possibility to combine with other strategies, for example soft or hard templating, to target even more sophisticated hierarchically meso–macroporous materials with specific structure and function for various applications has been presented. The “hierarchical catalysis” concept has been re-visited.