Hydrogen is a sustainable fuel option and one of the potential solutions for the current energy and environmental problems. Its eco-friendly production is really crucial for better environment and sustainable development. In this paper, various types of hydrogen production methods namely solar thermal (high temperature and low temperature), photovoltaic, photoelecrtolysis, biophotolysis etc are discussed. A brief study of various hydrogen production processes have been carried out. Various solar-based hydrogen production processes are assessed and compared for their merits and demerits in terms of exergy efficiency and sustainability factor. For a case study the exergy efficiency of hydrogen production process and the hydrogen system is discussed in terms of sustainability. (C) 2009 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.