A process for generating hydrogen gas from polyethylene (PE) by milling and heating with Ni-doped layered double hydroxide (LDH), which was prepared also by a mechanochemical route of two-step milling operation, was reported in this work. A mixture of PE and the prepared Ni-doped LDH was first milled in a planetary ball mill for 1 h followed by heating the milled product to 700 degrees C under He/Ar gas environment for hydrogen emission. Characterizations by a set of analytical methods of X-ray diffraction (XRD), thermogravimetry-mass spectroscopy (TG-MS) and gas chromatography (GC) were performed on the milled and heated samples to monitor the process. Gaseous products obtained during heating mainly consisted of H-2, CH4, CO, CO2 with H-2 concentration over 80% between 450 and 550 degrees C. Such a process could be developed to treat hydrocarbon based solid wastes for hydrogen generation. (C) 2009 Elsevier B.V. All rights reserved.