Hierarchically ordered structures facilitate the incorporation of diverse functions simultaneously. The present report introduces a simple and novel strategy for producing hierarchically ordered polymeric films. Hierarchical ordering of aqueous droplets on a polymer solution is realized by the imposition of physical confinement via various shaped gratings. After drying of the solution, well-ordered hierarchical structures were fabricated in the remaining polymer film. The size of the grating structure and the lattice size of spontaneous hexagonally packed aqueous pores comprise two different length scales, thereby offering multiscale ordering. Interfacial wetting of the polymer solution to the grating surface was crucial in terms of obtaining a highly ordered structure that can be tuned by dissolving a small amount of surfactant in the polymer solution. The present novel approach provides a new opportunity for lithography-free fabrication of complex hierarchical structures.