We demonstrate a simple route to fabricate hierarchical structures by combining the electrospinning technique and the wetting of porous templates. Poly(methyl methacrylate) (PMMA) fibers are first prepared by electrospinning and are collected on a glass substrate. The PMMA fibers are then brought into contact with an anodic aluminum oxide template. Upon thermal annealing above the glass transition temperature of PMMA, wetting of the polymer chains into the nanopores occurs. After the removal of the AAO template, ordered arrays of nanorods on polymer fibers are obtained. This approach is also applied to polystyrene (PS), and similar structures are obtained. This work provides a promising approach to fabricate hierarchical polymer structures with sizes that can be controlled over the nanoscopic and microscopic length scales.