The sister technologies, electrospinning and electrospraying provide a facile and universal synthesis method for the continuous preparation of nanostructured materials. Through adjusting the synthesis parameters, rich electrospun and electrosprayed nanomaterials, scaffolds, membranes with tunable composition (inorganic, polymeric, hybrid, etc.), shape (sphere, films, scaffold, etc.), morphology and inner structure (solid, hollow, core-shell, co-axial, etc.) can be selectively elaborated. This review provides an overview of the design of functional nanostructured materials, porous scaffolds and membranes by electrospinning and electrospraying techniques. Key experimental parameters and synthesis strategy are emphasized to reveal the synthesis-component-structure-property relationship and eventually realize the targeted functions through predictable synthesis. Potential applications in tissue engineering, medicine, membrane filtration and lithium battery are highlighted.