An electrohydrodynamic spray apparatus includes a liquid inlet and a spray nozzle in fluid communication with the liquid inlet, where the spray nozzle has an opening downstream of the liquid inlet. An inner electrode is situated at least partially inside the spray nozzle. An outer electrode is situated external to the spray nozzle and within about 100 mm of the opening of the nozzle. The electrohydrodynamic spray apparatus can be combined with a substrate to form an electrohydrodynamic spray system. The electrohydrodynamic spray apparatus or system can be used to form nanostructures such as nanodrops, nanoparticles and thin films.