Porous structures with sizes between the submicrometer and nanometer scales can be produced using efficient and adaptable electrospinning technology. However, to approximate desirable structures, the construction lacks mechanical sophistication and conformance and requires three-dimensional solitary or multifunctional structures. The diversity of high-performance polymers and blends has enabled the creation of several porous structural conformations for applications in advanced materials science, particularly in biomedicine. Two promising technologies can be combined, such as electrospinning with 3D printing or additive manufacturing, thereby providing a straightforward yet flexible technique for digitally controlled shape-morphing fabrication. The hierarchical integration of configurations is used to imprint complex shapes and patterns onto mesostructured, stimulus-responsive electrospun fabrics. This technique controls the internal stresses caused by the swelling/contraction mismatch in the in-plane and interlayer regions, which, in turn, controls the morphological characteristics of the electrospun membranes. Major innovations in 3D printing, along with additive manufacturing, have led to the production of materials and scaffold systems for tactile and wearable sensors, filtration structures, sensors for structural health monitoring, tissue engineering, biomedical scaffolds, and optical patterning. This review discusses the synergy between 3D printing and electrospinning as a constituent of specific microfabrication methods for quick structural prototypes that are expected to advance into next-generation constructs. Furthermore, individual techniques, their process parameters, and how the fabricated novel structures are applied holistically in the biomedical field have never been discussed in the literature. In summary, this review offers novel insights into the use of electrospinning and 3D printing as well as their integration for cutting-edge applications in the biomedical field.