This work discusses an alternative process option for the treatment of polyvinyl chloride (PVC) by producing hydrogen (H-2) gas, at the same time fixing chlorine for proper environmental control. In the first-stage, a milling operation is performed in a planetary ball mill to obtain a mixture of PVC sample with CaO and Ni(OH)(2) to be used as feed in the second-step, involving heating of the milled product. Analyses by thermogravimetry-mass spectroscopy (TG-MS) and gas chromatography (GC) showed H-2, CH4, CO and CO2 as main constituents. The results clearly show that addition of Ni(OH)(2) to provide nickel as catalyst and CaO as adsorbent to fix CO2 and HCl gases generated during heating, assisted in clean H-2 generation with concentration near 90% at temperatures between 450 and 550 degrees C. Analyses of solids after heating by X-ray diffraction and TG-DTA techniques showed both CaOHCl and CaCO3 as main phases in the product. This process could be developed to treat PVC wastes together with other polymers and/or plastic wastes for production of H-2 gas. (C) 2009 Elsevier B.V. All rights reserved.