Electrospray technique has been used in previous works as an excellent way to develop ordered nanostructures. This work focuses on the necessary conditions to achieve 3D nano-ordered layers, which are mainly determined by the conductivity of the liquid where nanoparticles are solved and the existence of an electrical field gradient. Changes in the conductivity induce a different evaporation rate during the ejection phase and control the amount of liquid that is deposited on the substrate. Controlling the conductivity, the electrical field and the quantity of liquid on the substrate different nanostructures can be fabricated, ranging from a semicovered monolayer of scattered nanoparticles up to a fully 3D colloidal crystal.