Electrospinning is a versatile technique and has been used to produce porous fibers ranging from submicron to nanometer in diameter. Using a variety of high-performance polymers and blends, several new configurations are, now, possible for applications in tactile sensing, energy harvesting, filtration, and biomedical technologies. The structures, however, lack desired mechanical conformity, complexity, and single/multi-material three-dimensional rigid constructs essential to mimic specific functionalities. A simple, yet versatile, strategy is by employing a digitally controlled fabrication process of shape-morphing called 3D printing/additive manufacturing process and by conjoining the two promising technologies. Thus, using strategic and hierarchical integration of processes, elaborate shapes, and patterns can be fabricated on mesostructured stimuli-responsive electrospun membranes. The focus of this investigation is primarily on biomedical structures, as part of a large effort of precision and advanced manufacturing for rapid prototyping.