CdSe/ZnS nanocrystals have been assembled into mesoscale structures (see Figure). Templates with dimensions down to 100 nm are generated via phase-shifting photolithography using composite poly(dimethylsiloxane) masks. Upon removal of the template, the CdSe/ZnS structures are found to exhibit hierarchical order over square nanometers (self-assembly of nanocrystals), square micrometers (template shape), and square centimeters (arrays of template pattern).