The self-assembly of ultrathin nanocrystals (UTNCs) into well-organized multidimensional superstructures is one of the key topics in material chemistry and physics. Highly ordered nanocrystal assemblies also known as superstructures or synthetic structures have remained a focus for researchers over the past few years due to synergy in their properties as compared to their components. Here, we aim to present the recent progress being made in this field with highlights of our research group endeavors in the engineering of self-assembled complex multidimensional superstructures of various inorganic materials, including polyoxometalates. The driving forces for the assembly process and its kinetics along with the potential applications associated with these unique ordered and spatially complex superstructures are also discussed.