Currently, the environmental deterioration and energy shortage issues have appealed tremendous attention by scientists. The new technologies and devices to alleviate these problems such as catalysis, photocatalysis, and electrocatalysis have been intensively explored. In these regards, the exploitation of highly efficient materials is a core factor to achieve the goal of substituting traditional fuels with sustainable and clean energy, and achieve efficient pollutants treatment. As an important class of nano-structured materials, hierarchically porous semiconductor materials have aroused significant attention during the past decade. Compared with bulk materials, hierarchically porous semiconductor materials materials possess a series of merits including large specific surface area, rich surface active sites, convenient mass transportation channels. These intrinsic advantages ensure hierarchically porous semiconductor materials with huge application potentials in photocatalytic pollutants treatment and sustainable energy production.