We report on the behavior of nanometric LiMn1/3Ni1/3Co1/3O2 (LiMNC) as a cathode material for Li-ion batteries in comparison with the same material with submicrometric particles. The LiMNC material was produced by a self-combustion reaction, and the particle size was controlled by the temperature and duration of the follow-up calcination step. X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared, Raman spectroscopy, electron paramagnetic resonance, inductively coupled plasma, and atomic force microscopy were used in conjunction with standard electrochemical techniques (cyclic voltammetry, chronopotentiometry, and electrochemical impedance spectroscopy) for characterizing the electrode materials. The effect of cycling and aging at 60 degrees C was also explored. Nanomaterials are much more reactive in standard electrolyte solutions than LiMNC with a submicrometric particle. They develop surface films that impede their electrochemical response, while their bulk structure remains stable during aging and cycling at elevated temperatures. The use of nanomaterials in Li-ion batteries is discussed. (C) 2009 The Electrochemical Society. [DOI: 10.1149/1.3212850] All rights reserved.