The development of synthetic methods for micro/nano materials with precisely controlled structures, morphologies, and local compositions is of great importance for the advancement of modern nanotechnology. The electrospray method is a "platform" approach for the preparation of a broad range of micro-/nanostructures; electrospray is simple and scalable. This review summarizes recent research on the micro-/nanostructures prepared via the electrospray route. These include spherical structures (e.g. simple, porous, Janus, and core-shell particles), non-spherical structures (e.g. red blood cell-like and spindle-like particles, multi-compartment microrods, 2D holey nanosheets, and nanopyramids), and assembled structures. The experimental details, underlying physical/chemical principles, and key benefits of these structures are comprehensively discussed. The effects and importance of nozzle design, properties of feeding solutions (e.g. concentration of solute, polymer additives, solvent/nonsolvent combinations), working environment (e.g. temperature and humidity), and types of collection media are highlighted.