Sub-2-nm (down to one-unit cell) uniform oxide nanocrystals and highly ordered superstructures were obtained in one step using oleylamine and oleic acid as capping and structure directing agents. The cooperative nature of the nanocrystal growth and assembly resulted in mesoscopic one-dimensional ribbon-like superstructures made of these ultrathin nanocrystals. The process reported here is general and can be readily extended to the production of many other transition metal (TiO2, ZnO, Nb2O5) and rare earth oxide (Eu2O3, Sm2O3, Er2O3, Y2O3, Tb2O3, and Yb2O3) systems.