The stringent COx-free hydrogen requirement for the current low temperature fuel cells has motivated the development of COx-free hydrogen production alternatives to the conventional hydrogen production technologies. Recently, our group has investigated step-wise reforming of hydrocarbons and catalytic decomposition of ammonia for COx-free production of hydrogen. These investigations have employed conventional surface science techniques, model catalysts as well as high surface area supported metal catalysts. This paper presents an overview of the studies undertaken in our laboratory and highlights the important aspects of the proposed CO-free hydrogen production processes.