A single-step approach for the synthesis of multi-walled nanotubes (MWNT) filled with nanowires of Ni/ternary Zr based hydrogen storage alloy has been illustrated. We also demonstrate the generation of COfree hydrogen by methane decomposition over alloy hydride catalyst. The present work also highlights the formation of single-walled nanotubes (SWNT) and MWNTs at varying process conditions. These carbon nanostructures have been characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution TEM (HRTEM), Energy dispersive X-ray analysis (EDX) and Raman spectroscopy. This new approach overcomes the existing multi-step process limitation, with possible impact on the development of future fuel cell, nano-battery and hydrogen sensor technologies.