Electrostatic spray pyrolysis has been used to produce high voltage LiNi0.5Mn1.5O4 thin film electrodes for 3D Li-ion microbattery application. The influence of the synthesis parameters on the structure, texture and electrochemical behavior of the produced electrode has been investigated using X-ray diffraction, scanning and transmission electron microscopies, cyclic voltammetry and galvanostatic measurements. A specific capacity of 135 mAh.g(-1) can be achieved without any electronic conducting additive in the electrode. Moreover, a controlled deposition on a flat and 3D architecture substrate has been demonstrate and discussed showing the potential of such a deposition technique in the production of 3D all solid state Li-ion batteries. (C)2011 Elsevier B.V. All rights reserved.