The self-assembly of anisotropic particles into two or three dimensional ordered arrays has diverse applications in several areas of science and engineering. In this article, we report the formation of a multi-layer film of nano-sized ellipsoids with long-range orientation and positional order through an evaporation driven vertical deposition technique. Using nano-sized ellipsoids of tunable surface charge, we show that electrostatic interactions can be exploited to control the arrangement of ellipsoids in the film. The pH of the aqueous suspensions used for vertical deposition is adjusted such that the surface charge and hence the electro-static interactions can be controlled. We show that the interplay between various Derjaguin and Landau, Verwey and Overbeek (DLVO) interactions can be effectively controlled to fabricate films with a random arrangement of particles as well as to create particulate films with three-dimensional ordering of ellipsoids. When the particles are weakly charged, the nano-ellipsoids in the film are randomly oriented giving an amorphous particulate film. However, when the particles are highly charged, the nano-ellipsoids in the film are oriented with major axis parallel to each other and ordered in three dimensions. These particulate film are observed to have parallel cracks across the entire width of the film. The major axis of the particle is found to be parallel to the crack direction and therefore, the direction of crack formation can be exploited to indicate the nature of particle ordering. © The Royal Society of Chemistry 2015.