Mesoporous metal-based materials (MMBMs) have received unprecedented attention in catalysis, sensing, and energy storage and conversion owing to their unique electronic structures, uniform mesopore size and high specific surface area. In the last decade, great progress has been made in the design and application of MMBMs; in particular, many novel assembly engineering methods and strategies based on amphiphilic block copolymers as structure-directing agents have also been developed for the "bottom-up" construction of a variety of MMBMs. Development of MMBMs is therefore of significant importance from both academic and practical points of view. In this review, we provide a systematic elaboration of the molecular assembly methods and strategies for MMBMs, such as tuning the driving force between amphiphilic block copolymers and various precursors (i.e., metal salts, nanoparticles/clusters and polyoxometalates) for pore characteristics and physicochemical properties. The structure-performance relationship of MMBMs (e.g., pore size, surface area, crystallinity and crystal structure) based on various spectroscopy analysis techniques and density functional theory (DFT) calculation is discussed and the influence of the surface/interfacial properties of MMBMs (e.g., active surfaces, heterojunctions, binding sites and acid-base properties) in various applications is also included. The prospect of accurately designing functional mesoporous materials and future research directions in the field of MMBMs is pointed out in this review, and it will open a new avenue for the inorganic-organic assembly in various fields.