Porous materials have played an increasingly critical role in materials sciences and chemistry. From the viewpoint of applications, highly crystallized mesoporous architectures are very promising mainly due to their unique properties arising from the crystallized frameworks and many exciting applications in diverse fields. In this Highlight article, we summarize recent innovative researches in the creation of mesoporous architectures possessing crystalline pore walls. In particular, new strategies to synthesize highly crystallized mesoporous metals and metal oxides, metal–organic frameworks with large-sized mesopores, and zeolites with hierarchical mesoporosity are described. These mesoporous architectures show a lot of promise in energy and environment-related areas.