Electrospraying utilises electrical forces for liquid atomisation. Droplets obtained by this method are highly charged to a fraction of the Rayleigh limit. The advantage of electrospraying is that the droplets can be extremely small, down to the order of 10's nanometres, and the charge and size of the droplets can be controlled to some extent be electrical means. Motion of the charged droplets can be controlled by electric field. The deposition efficiency of the charged spray on an object is usually higher than that for uncharged droplets. Electrospray is, or potentially can be applied to many processes in industry and in scientific instruments manufacturing. The paper reviews electrospray methods and devices, including liquid metal ion sources, used for thin film deposition. This technique is applied in modern material technologies, microelectronics, micromachining, and nanotechnology.