Very recently, ultrathin perovskite nanostructures, with the advantages of perovskite and ultrathin properties, have received an enormous level of interest due to their many fascinating properties, such as a strong quantum confinement effect and a large specific surface area. In spite of this incredible success of perovskite nanocrystals (NCs), the development of perovskite NCs is still in its infancy, and the production of high-quality ultrathin perovskite nanostructures has been a hot topic in the fields of nanoscience and nanotechnology. Herein, we demonstrate that ultrathin CsPbBr3 perovskite nanosheets (NSs) can be obtained by a simple mixing of precursor-ligand complexes under ambient conditions. It was found that the formation of NSs is ascribed to the stepwise self-assembly of the initially formed different types of ultrathin nanostructures. Due to the disappearance of grain boundaries and protection of branched ligands, these NSs exhibit enhanced optical properties compared to other types of samples. This direct synthesis method opens up a promising road for the synthesis of ultrathin NSs and guides the fabrication of other ultrathin nanostructures.