This paper reported a new pretreatment of silicone penetrant for forming the chromium-free chemfilm (chemical conversion coating) on the surface of an AZ91D magnesium (Mg) alloy. Through applying micro current on the pretreatment solution, an uniform mask membrane was created on the surface of a Mg alloy. By using X-ray diffraction (XRD), scanning electron microscope (SEM), and Energy Dispersive Spectrometer (EDS) analyses, the chromium-free chemfilm on a Mg alloy was examined to analyze the performance during initial, middle, and final deposition periods. As a result, the pretreatment of silicone penetrant can effectively prevent the chemfilm from cracking, improve the anticorrosion ability and nucleation rate of the chromium-free chemfilm on a Mg alloy, and make the surface crystallization transform a long strip into short axis shape. (C) 2016 Elsevier B.V. All rights reserved.