Aprotic PYR14TESI (1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)) ionic liquid served to develop a new electrochemical route for one-step deposition of NiO from PYR14NO(3) reduction (1-butyl-1-methylpyrrolidinium nitrate) in a Ni(TFSI)(2) (Nickel (II) bis(trifluoromethanesulfonyl)imide) containing electrolyte. The high solubility of the novel PYR14NO(3) salt in PYR14TFSI (>0.1 M) in comparison with other oxygenated precursors such as oxygen gas, NaNO3 or KNO3 (i.e. 10-15 mM) allows the formulation of a broad variety of electrolytes which opens wide possibilities to tune the physico-chemical properties of NiO films (e.g. morphology: from flat to nanostructured films). Furthermore, electrochemical deposition in an electrolyte containing low water concentration (>30 ppm by Karl Fisher titration) served to demonstrate that only a small amount of moisture dramatically affects the electrochemical reduction of NO3-, resulting in OH- generation close to the cathode and subsequent NiO(OH)/Ni(OH)(2) deposition, as proved by X-ray diffraction and X-ray photoelectron spectroscopy. This finding highlights the importance of aprotic ionic liquids in developing a general electrochemical route for metal oxide deposition without the formation of metal hydroxide species, thus avoiding the requirement for post-deposition annealing treatments. The versatility of the present deposition route as well as its impact in (opto)electronic devices was pointed out by the successful preparation of nanostructured n-p ZnO/NiO heterojunctions exhibiting rectifying current-voltage characteristics. (C) 2013 Elsevier Ltd. All rights reserved.