Macroporous and hierarchically macro/mesoporous materials (mostly monoliths and microspheres) have attracted much attention for a variety of applications, such as supporting or enabling materials in chromatography, energy storage and conversion, catalysis, biomedical devices, drug delivery systems, and environmental remediation. A well-succeeded method to obtain these tailored porous materials relies on the sol-gel technique, combined with phase separation by spinodal decomposition, and

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... as well emulsification as a soft template, in the case of the synthesis of porous microspheres. Significant advancements have been witnessed, in terms of synthesis methodologies optimized either for the use of alkoxides or metal–salts and material design, including the grafting or immobilization of a specific species (or nanoparticles) to enable the most recent trends in technological applications, such as photocatalysis. In this context, the evolution, in terms of material composition and synthesis strategies, is discussed in a concerted fashion in this review, with the goal of inspiring new improvements and breakthroughs in the framework of porous materials.