In this paper we introduce the electrospray technique as a suitable method to create SiO2 3D ordered nanostructures. We describe the experimental procedure and deposition parameters required. We have found that the use of a high electric field is mandatory to, first, induce the Taylor cone and then, to get 3D order while the nanospheres assemble in the substrate in the drying phase. (C) 2014 Elsevier B.V. All rights reserved.