The properties and performance of solid nanomaterials in heterogeneous chemical reactions are significantly influenced by the interface between the nanomaterial and environment. Oriented tailoring of interfacial dynamics, that is, modifying the shared boundary for mass and energy exchange has become a common goal for scientists. Although researchers have designed and constructed an abundance of nanomaterials with excellent performances for the tailoring of reaction dynamics, a complete understanding of the mechanism of nanomaterial-environment interfacial interaction still remains elusive. To predictively understand the nanomaterial-environment relationship over a wide range of time scale, a deep and dynamic insight is required urgently. In this Account, our recent works including advances in the design and construction of nanoassembled interfaces and understanding the dynamic interaction mechanisms between different combinations of nanoparticle (NP) assembly environment interfaces for tailoring the reaction dynamics.NP assemblies with well-defined structures and compositions are inherently suitable for replacing bulk-type nanomaterials for the research on interfaces. We primarily introduced two most relevant nanoassembled surfaces that were fabricated in our laboratory, namely, ordered self-assembly interface and animate nanoassembled interface. The disordered nanoparticles can be arranged into an ordered superlattice based on the self-assembly method and patterned-assembly method. In addition, we used NPs with flexible properties to construct three-dimensional (3D) animate assemblies. On the basis of a thorough understanding of the structure-property correlation, a series of nanoassembled interfaces with various structures have been developed for practice. In comparison with traditional nanomaterial-environment interfaces, the nanoassembled interfaces can change the mode of contact between the nanomaterial and environment, thereby maximizing the number of active sites and driving interferent/product off the nanoassembled interface. The geometry, porosity, and deformable/motional properties in the nanoassembled interface can be applied to enhance the mass transfer dynamics in the chemical reaction. Moreover, the nanoassembled interface can be used to strengthen the affinity between the NP assemblies and targets, thereby enhancing the adsorption efficiency. As shown in these examples, the nanoassembled interface can effectively change the speed, intensity, and mode of interactions between the NP assemblies and environment in spatiotemporal scales.The overall performance of the interfacial dynamics can be improved by the nanoassembled interface, thereby facilitating practical application in flowing systems. We have extended the applications of nanoassembled interfaces from simple adsorption to complex reactions in flowing systems, including in vivo magnetic resonance imaging, electrocatalytic gas evolution reaction, bacterial capture, sensing of exhaled volatile organic compounds, and heterogeneous catalysis. Our current endeavors to explore the applicability of animate nanoassembled interfaces for dynamic tailoring have widened the scope of research, and attempts to construct intelligent interfaces for applications are underway.