The microstructure (composition, size and shape etc.) of semiconductor nanocrystals determine the electronic density of states of semiconductor nanomaterials and ultimately determine their optical and electrical properties. Semiconductor nanocrystal advanced structures, such as hybrid nanostructures and nanocrystal superlattices, not only integrate the function of individual nanocrystals, but also brings the materials collective and synchronic properties. How to control the monodispersity, composition and structure of as-prepared semiconductor nanocrystals during their syntheses, as well as their furthermore assembly, has been a hot research area in this decade. This critical review focuses on the development of synthetic and assembly methods (techniques) of semiconductor nanocrystals processed in the liquid phase. Emphasis is on the synthesis methodology, microstructure related properties of semiconductor nanocrystals, and their applications (243 references).