Hierarchically porous materials have attracted great attention because of their potential applications in the fields of adsorption, catalysis, and biomedical systems. The art of manipulating different templates that are used for pore construction is the key to fabricating desired hierarchically porous structures. In this feature article, the polyelectrolyte-surfactant mesomorphous complex templating (PSMCT) approach, which was first developed by our group, is elaborated on. During the organic-inorganic self-assembly, the mesomorphous complex of the polyelectrolyte and oppositely charged surfactants would undergo in situ phase separation, which is the key to fabricating hierarchically porous materials. The recent progress in the utilization of the PSMCT method for the synthesis of hierarchically porous materials with tunable morphologies, mesophases, pore structures, and compositions is reviewed. Meanwhile, the functions of the hierarchically porous materials synthesized by the PSMCT method and their applications in adsorption, catalysis, drug delivery, and nanocasting are also briefly summarized.