This chapter presents an overview of the synthesis strategies based on the sol-gel process for the preparation of multimodal porous networks of hierarchically structured functional materials and a brief introduction to their applications as photocatalysts, scaffold templates, and catalyst supports. Until now, many successful examples have been reported for the preparation of hierarchically porous materials by combining a single templating method with a supplementary chemical or physical method. The chapter provides an introduction to the synthesis strategies for the preparation of hierarchically porous materials using the dual and multiple micellar templates in hierarchically porous material synthesis. It reviews the features and history of self-formation phenomenon to target hierarchically structured porous materials based on metal alkoxides. The chapter also reviews the effects of general synthesis conditions on the self-formation phenomenon, including metal alkoxide, surfactant, solvent, pH values, and hydrothermal synthesis.