Electrochromic (EC) performances of Ni3+ containing NiO thin films, called modified NiO thin films, prepared either by pulsed laser deposition or by chemical route are reported. When cycled in lithium based electrolyte, the comparison of the EC behavior of nonstoichiometric NiO thin films points out a larger optical contrast for the films synthesized by chemical route with the absence of an activation period on early electrochemical cycling due in particular to a larger porosity. Herein we demonstrate faster kinetics for modified NiO thin films cycled in lithium ion free electrolyte. Finally, X-ray absorption spectroscopy is used for a preliminary understanding of the mechanism involved in this original EC behavior linked to the film characteristics including their disorder character, the presence of Ni3+ and their porous morphology. (C) 2013 Elsevier B. V. All rights reserved.