Nanocrystals (NCs) and their assembled superlattices (SLs) enable the study of mesoscale phenomena and rational design of metamaterials for a broad range of applications. The diverse array of building blocks, encompassing core design and surface ligands, made NCs artificial atoms. However, grand challenges arise from the limited mobility of NC building blocks in dried NCSLs, restricting their potential in fabrication and post-treatment. Capturing the dynamic structure in heterodimer assembly and exploring thermal responsive NCSL formations will further expand the broad applications of NCSLs. Three major levels of design will be discussed, including the core, ligand, and assembly environment. Multicomponent NCSLs can be built by anisotropic heterodimer nanocrystals in addition to the binary and ternary NCSLs. These asymmetric NCs evolve into an aligned phase where the orientation of heterodimers is constrained in octahedral voids. During the assembly, dynamic rotator phase intermediates, reminiscent of plastic crystals, can be observed using in situ techniques. This phase-transition behavior holds potential akin to phase-transferrable materials. Moreover, the common solvent evaporation approach lacks control and reversibility. Tailored promesogenic ligands, exhibiting a lubricating property, are introduced to address this issue in dry NCSLs. The lubricating ability of ligands is thermally triggerable, facilitating the dry solid NC random aggregates to transform into NCSLs with preferred orientations. The principles, kinetics, and utility of lubricating ligands could provide methodological strategies to unlock stimuli-responsive metamaterials from NCSLs and further contribute to the fabrication of NCSLs. Reversible design from the environment is conducted with liquid crystal as a ‘smart solvent.’ In their isotropic phase, NCs can disperse, resembling traditional solvents used in colloidal NC research; however, cooled LCs expel NCs, which can drive NCs assembly into NCSLs. This fully reversible growth method can be considered as cooling crystallization of NCs from LCs. The improved control over the NC self- assembly process can be potentially used in separation and purification. The diverse growth mode and the morphologies of NCSLs will pave the way for the ‘colloidal synthesis’ of NCSL clusters and liquid-phase epitaxy of mesoscale crystals. This thesis will discuss the utility of both functional NCs and their self-assembled SLs. The NCs could inherently be used as catalysts due to their high surface exposure. The self-assembly can help to fabricate metamaterials when NCs are considered as precursor to build optical metamaterials. Furthermore, NCs are capable to form meta-atoms and metamolecules in the constrained environments. This capacity for using NCs to generate novel structures facilitates advancements in energy and optical applications. Dynamic NCSLs, which remains underexplored, should be capable of adapting to these applications in the future.