Creating an ordered three-dimensional hierarchical structure using nanoimprint lithography remains a challenge even though such structures with micro-/nanometer scale are important with technological advances in a number of applications. The controllable polyimide (PI) hierarchical structures could be obtained by using polyamic acid (PAA) precursor in gamma-butyrolatone-N-methylpyrrolidone mixture solution of various concentrations (1, 2, 3, and 4 wt %) through dewetting in an imprinting process. PI patterns without a residual layer are formed due to the dewetting phenomena caused by the surface tension, and thus formed patterns of different ambits are obtained due to the fluidity of the PAA solutions. This method is not restricted to a specific polymer and substrate and could be easily applied to pattern other organic materials.